CN109959684A - Preparation, the remaining method of the detection dead tick of vegetable poisoning and the detection device of double identification type chlopyrifos sensors - Google Patents
Preparation, the remaining method of the detection dead tick of vegetable poisoning and the detection device of double identification type chlopyrifos sensors Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of the double identification type chlopyrifos sensors of enzyme-molecular engram based on nano-perovskite material, i.e. MIP/ITO/CH3NH3PbI3The preparation of the bis- identification type sensors of/CS/AChE.The invention also discloses detection the remaining method of the dead tick of vegetable poisoning, specifically: a, make chlopyrifos concentration and electric current linear relationship chart: b, test sample Chlorpyrifos concentration: measurement obtain the inhibition photo-signal value of chlopyrifos solution to be measured；Using the chlopyrifos concentration of production and the linear relationship chart of inhibition photoelectric current, the inhibition photo-signal value of chlopyrifos solution to be measured is obtained with measurement, obtains chlopyrifos solution Chlorpyrifos concentration to be measured.The present invention discloses a kind of remaining device of the dead tick of detection vegetable poisoning, including electrochemical workstation, light source, electrolytic cell, working electrode, reference electrode and auxiliary electrode again.The present invention can detect the dead tick residual of vegetable poisoning, and testing cost is low, selectivity is good, sample pre-treatments are simple, easy to operate and sampling amount is small.
Description
Technical field
The present invention relates to one kind be based on electrochemical method, in particular to a kind of remaining method of the dead tick of detection vegetable poisoning,
The double identification type chlopyrifos sensors of enzyme-molecular engram based on nano-perovskite material.
Background technique
Chlopyrifos (Chlorpyrifos, CPF) is common a kind of organophosphorus insecticide in agricultural, can destroy cholinester
Enzyme simultaneously causes choline function obstacle even dead, to jeopardize the safety of human and animal.Organophosphorus pesticide makes in limitation agricultural
Dosage and be forbidden to use toxic organophosphorus pesticide be it is most important, by global extensive concern.Recently, some toxic
Organophosphorus pesticide, such as parathion and parathion-methyl, forbidden by Environmental project planning administration and food agricultural organization or
Stringent limitation uses.2000, Japanese Ministry of Health, Labour and Welfare regulation indoor air quality chlopyrifos concentration should be not more than 1000ng/
m3, children's room air is less than 100ng/m3.Highest residual limit of the chlopyrifos in vegetables is defined in Japan positive list system
Magnitude is 0.01~0.5mg/kg, and the maximum residue limit value in pollution-free vegetable as defined in China is 1mg/kg, therefore is established
A kind of accurate, easy, system the dead tick detection method of content of vegetable poisoning is of great significance.
Before making the present invention, commonly the method for detection chlopyrifos is mostly that chromatography and other technologies are combined.Using chromatography
Method can improve the sensitivity and selectivity of analysis, but instrument uses more complex and higher cost, sample extraction purifying step phase
To cumbersome, sensitivity by sample purification, concentration and etc. influenced, and these methods are more demanding to instrument and equipment.
Summary of the invention
The object of the present invention is to provide a kind of preparations of double identification type chlopyrifos sensors, the dead tick residual of detection vegetable poisoning
Method and detection device, testing cost of the present invention is low, sample pre-treatments are simple, easy to operate and sampling amount is small.
The first purpose of this invention is achieved through the following technical solutions, the enzyme-point based on nano-perovskite material
The preparation method of the double identification type chlopyrifos sensors of sub- trace, comprising the following steps:
(1) preparation of perovskite precursor liquid
By CH3NH3I crystal and PbCl2Half an hour is mixed in DMF according to molar ratio 4:1 to get the calcium of brown is arrived
Titanium ore precursor liquid；
(2)ITO/CH3NH3PbI3The preparation of the bis- identification type sensors of/CS/AChE
Sheet is aoxidized cigarette tin ITO electro-conductive glass by (2-1), is put into containing 2mol L-1In the aqueous isopropanol of KOH, boil
30min is cleaned up in ultrapure water in middle ultrasound with ultrasonic wave, is dried for standby at 100 DEG C in an oven；
(2-2)ITO/CH3NH3PbI3The preparation of/CS/AChE sensor:
(2-2-1)ITO/CH3NH3PbI3The preparation of electrode: perovskite precursor liquid is equably spin-coated on ITO electro-conductive glass
On, obtain ITO/CH3NH3PbI3Electrode；
(2-2-2) molecular engram sensor (MIP) MIP/ITO/CH3NH3PbI3The preparation of/CS: by ITO/CH3NH3PbI3
Electrode is put into chitosan stock solution, and chitosan stock solution contains 1.0mmolL-1Chlopyrifos, with permanent electricity under conditions of -1.5V
Position sedimentation polymerize 5min, makes electrode surface while having polymerize chlopyrifos and chitosan；ITO/ is taken out after the completion of deposition
CH3NH3PbI3/ CS electrode drips the glutaraldehyde that volumetric concentration is 0.1% in ITO/CH3NH3PbI3/ CS electrode surface, after drying
Fall excessive glutaraldehyde with distilled water flushing, then dry, continues this electrode being immersed in 0.1molL-1In Klorvess Liquid, benefit
With the mode of cyclic voltammetry scan, template molecule elution is fallen, the potential region during cyclic voltammetry scan is -1.2~0.5
Electrode is taken out and is cleaned after the completion by V, and the electrode dried is exactly molecular engram sensor MIP/ITO/CH3NH3PbI3/
CS, there are the recognition sites of many chlopyrifos molecules on surface；
10 μ L CS/AChE hanging drops are coated onto clean molecular imprinting sensor MIP/ITO/CH by (2-2-3)3NH3PbI3/
It is on CS electrode and dry at 4 DEG C, obtain MIP/ITO/CH3NH3PbI3/ CS/AChE sensor.
Preferably, CH in the step (1)3NH3The preparation method of I crystal is: by methylamine (CH3NH2), hydroiodic acid (HI)
It is mixed at room temperature with ethanol solution, 1h is stirred in nitrogen environment, evaporation obtains crystal, washed 3 times with dimethyl ether, then by crystal
It puts 60 DEG C of dryings in a vacuum drying oven and for 24 hours, obtains white CH3NH3I crystal；CH3NH2: HI: ethyl alcohol (v/v/v)=12.54:
22.80:95.
Preferably, in the step (2-2-2) chitosan stock solution preparation method: chitosan is mixed with glacial acetic acid,
It stands overnight and adds chlopyrifos after becoming uniformly to be configured to homogeneous solution.
Preferably, the circle number of cyclic voltammetry scan is 50 circles in the step (2-2-3).
Preferably, in the step (2-2-4) CS/AChE suspension preparation method: 0.5g Chitosan powder is dissolved
In 100.0mL1.0% acetic acid solution, 5g/L chitosan CS solution is obtained, 10.0mg acetylcholinesterase is added,
It is gently mixed 15min at room temperature.
Second object of the present invention is achieved through the following technical solutions, and detects vegetable poisoning using the sensor
The remaining method of dead tick, comprising the following steps:
A, the linear relationship chart of chlopyrifos concentration and electric current is made:
(a-1) with MIP/ITO/CH3NH3PbI3/ CS/AChE sensor is working electrode, to be saturated potassium chloride electrode as ginseng
Than electrode, using platinum electrode as auxiliary electrode, 10mL is added in electrolytic cell and contains 0.6mmolL-1Acetyl chloride thiocholine
Phosphate buffer solution；Reference electrode and auxiliary electrode are respectively put into electrolytic cell；By MIP/ITO/CH3NH3PbI3/CS/
AChE working electrode is immersed respectively in various criterion concentration chlopyrifos to be taken out after 10min, then is inserted into electrolytic cell respectively, inclined
Current potential is set as under conditions of 0V, halogen light light source shines acetyl chloride thiocholine electrolyte from electrolytic cell from left to right
It penetrates, the photoelectric current that measurement obtains the chlopyrifos solution of different known concentrations respectively inhibits signal value；
(a-2) using the concentration of chlopyrifos solution as abscissa, inhibiting signal value with the photoelectric current of chlopyrifos solution is vertical sit
Mark, production chlopyrifos concentration and the linear relationship chart for inhibiting photoelectric current；
B, test sample Chlorpyrifos concentration:
(b-1) with MIP/ITO/CH3NH3PbI3/ CS/AChE sensor is working electrode, to be saturated potassium chloride electrode as ginseng
Than electrode, using platinum electrode as auxiliary electrode, 10mL is added in electrolytic cell and contains 0.6mmolL-1Acetyl chloride thiocholine
Phosphate buffer solution；Reference electrode and auxiliary electrode are respectively put into electrolytic cell；It is extracted from vegetables and obtains to be measured poison with poison
Tick solution, by MIP/ITO/CH3NH3PbI3/ CS/AChE working electrode immerses in chlopyrifos solution to be measured to be taken out after 10min, is inserted
Enter in electrolytic cell, under conditions of bias potential is 0V, halogen light light source to the right shines electrolyte from the left of electrolytic cell
It penetrates, measurement obtains the inhibition photo-signal value of chlopyrifos solution to be measured；
(b-2) using the linear relationship chart of the chlopyrifos concentration of production and inhibition photoelectric current, poison to be measured is obtained with measurement
The inhibition photo-signal value of dead tick solution, obtains chlopyrifos solution Chlorpyrifos concentration to be measured.
Preferably, vegetable sample ethyl alcohol dissolution filter.
Preferably, the concentration of the chlopyrifos solution of various criterion concentration described in the step (b-1) is at least three.
Third object of the present invention is achieved through the following technical solutions, and a kind of dead tick of detection vegetable poisoning is remaining
Device, electrochemical workstation, light source, electrolytic cell, working electrode, reference electrode and auxiliary electrode；
Working electrode, reference electrode and auxiliary electrode form three-electrode system, working electrode CH3NH3PbI3/CS/AChE
The electro-conductive glass of modification, i.e. MIP/ITO/CH3NH3PbI3/ CS/AChE sensor, reference electrode is saturation potassium chloride electrode, auxiliary
Helping electrode is platinum electrode；
Working electrode, reference electrode and auxiliary electrode are set in electrolytic cell；
Light source is set on the left of electrolytic cell；
CHI760D electrochemical workstation (Shanghai Chen Hua Instrument Ltd.) includes Survey Software and three electrode interfaces, and three
Electrode interface is separately connected working electrode, reference electrode and auxiliary electrode.
Preferably, the light source is halogen light light source, and halogen light light source is 250 watts；The electrolytic cell material is stone
English.
Compared with prior art, the invention has the following advantages:
First, MIP/ITO/CH3NH3PbI3/ CS/AChE sensor is to be based on molecular engram and the double identification type sensors of enzyme,
Selectivity is preferably；
Second, perovskite material is successfully applied to molecular engram and enzyme load carriers；
Third, vegetable sample ethyl alcohol dissolution filter.
Detailed description of the invention
Fig. 1 is MIP/ITO/CH of the present invention3NH3PbI3/ CS/AChE immerses 10min in the chlopyrifos solution of various concentration
Afterwards, containing 0.6mmolL-1The 0.1mol L of acetyl chloride thiocholine-1Photocurrent response figure in pH 7.0PBS；Fig. 1
In: represent chlopyrifos solution concentration (a) as 0nmol L-1；(b) chlopyrifos solution concentration is represented as 0.5nmol L-1；(c) generation
Table chlopyrifos solution concentration is 1.0nmol L-1；(d) chlopyrifos solution concentration is represented as 10.0nmol L-1；
Fig. 2 is MIP/ITO/CH of the present invention3NH3PbI3/ CS/AChE electrode is in 0.6mmolL-1Acetyl chloride thiocholine
Photocurrent response figure in solution, in Fig. 2: a → j refers to MIP/ITO/CH3NH3PbI3/ CS/AChE electrode immerses 0 respectively,
0.02,0.05,0.1,0.2,0.4,0.6,0.8,1.0 and 2.0nmol L-1Photocurrent response figure after chlopyrifos 10min；
Fig. 3 is the structural schematic diagram of the present invention detection remaining device of the dead tick of vegetable poisoning；
In figure: 1. auxiliary electrodes；2. working electrode (CH3NH3PbI3The electro-conductive glass of/CS/AChE modification)；3. reference is electric
Pole；4. saturated potassium chloride solution；5. electrolytic cell；6. the PBS solution containing acetyl chloride thiocholine；7 light sources；8 electrochemistry works
It stands；9 computers.
Specific embodiment
A kind of remaining method of the dead tick of detection vegetable poisoning, comprising the following steps:
A, the preparation of the double identification type chlopyrifos sensors of enzyme-molecular engram based on nano-perovskite material
The preparation of perovskite precursor liquid
By 33% methylamine (CH of 38mL concentration expressed in percentage by volume3NH2), 57% hydroiodic acid of 40mL concentration expressed in percentage by volume (HI) and
95% ethanol solution of 100mL concentration expressed in percentage by volume mixes at room temperature, and 1h is stirred in nitrogen environment, and evaporation obtains crystal, uses diformazan
Ether washs 3 times, is then placed on 60 DEG C of dryings in vacuum oven and for 24 hours, obtains white CH3NH3Then I crystal will obtain
CH3NH3I crystal and PbCl2Half an hour is mixed in DMF according to molar ratio 4:1 to get the perovskite precursor liquid of brown is arrived.
ITO/CH3NH3PbI3The preparation of the bis- identification type sensors of/CS/AChE
Oxidation cigarette tin (ITO) electro-conductive glass is cut into sheet, is put into containing 2mol L-1In the aqueous isopropanol of KOH, boil
30min is cleaned up in ultrapure water in middle ultrasound 10min with ultrasonic wave, is dried for standby at 100 DEG C in an oven.
ITO/CH3NH3PbI3The preparation of/CS/AChE sensor:
(1)ITO/CH3NH3PbI3The preparation of electrode: 50 μ L of perovskite precursor liquid is taken equably to be spin-coated on ITO electro-conductive glass
On, obtain ITO/CH3NH3PbI3Electrode.
(2) molecular engram sensor MIP/ITO/CH3NH3PbI3The preparation of/CS: chitosan stock solution (by 2g chitosan with
2% glacial acetic acid mixes and is settled to 50mL, stands overnight and weighs the chlopyrifos that 0.0175g is added after becoming uniformly again to configure
At homogeneous solution) in be put into above-mentioned ITO/CH3NH3PbI3Working electrode, the stock solution contain 1.0mmolL-1Chlopyrifos ,-
It polymerize 5min with potentiostatic electrodeposition method under conditions of 1.5V, make electrode surface while has polymerize chlopyrifos (Chlorpyrifos, letter
Claim CPF) and chitosan (Chitosasn, abbreviation CS) (electropolymerization).Electrode is taken out after the completion of deposition, by concentration expressed in percentage by volume
It drips for 0.1% appropriate glutaraldehyde in electrode surface, falls excessive glutaraldehyde with distilled water flushing after drying, then dry, continue
This electrode is immersed in Klorvess Liquid (0.1molL-1) in, in the way of the circle of cyclic voltammetry scan 50, by template molecule
It washes away, potential region in the process is -1.2~0.5V, and electrode is taken out and cleaned after the completion, the electrode dried is exactly
Molecular engram sensor (MIP/ITO/CH3NH3PbI3/ CS), there are the recognition sites of many chlopyrifos molecules on surface.
(3) chitosan solution (0.5%) (w/v) is dense by the way that 0.5g Chitosan powder is dissolved in 100.0mL volume basis
It spends in 1.0% acetic acid solution and is prepared, add 10.0mg acetylcholinesterase (AChE), be gently mixed at room temperature
15min obtains CS/AChE suspension.The above-mentioned CS/AChE hanging drop of 10 μ L is coated onto clean MIP/ITO/CH3NH3PbI3/CS
On electrode and dry at 4 DEG C, the electrode obtained is marked as MIP/ITO/CH3NH3PbI3/CS/AChE。
B, the linear relationship chart of chlopyrifos concentration and electric current is made:
(1) CH is modified in clean conductive glass surface according to the above method3NH3PbI3After/CS/AChE, it is placed at 4 DEG C and dries in the air
It is dry, working electrode, i.e. MIP/ITO/CH is made3NH3PbI3/ CS/AChE modified electrode；
(2) 10mL is added in electrolytic cell and contains 0.6mmolL-1The phosphate buffer solution of acetyl chloride thiocholine,
Measure the photoelectric current of modified electrode；
(3) modified electrode is immersed in various criterion concentration chlopyrifos respectively and is taken out after 10min, then insertion 10mL contains respectively
There is 0.6mmolL-1In the electrolytic cell of the phosphate buffer solution of acetyl chloride thiocholine, photoelectric current is measured.
With MIP/ITO/CH3NH3PbI3/ CS/AChE electrode is working electrode, to be saturated potassium chloride electrode as reference electrode,
Using platinum electrode as auxiliary electrode, working electrode, reference electrode and auxiliary electrode are respectively put into electrolytic cell；It is set on the left of electrolytic cell
Set halogen light light source；Under conditions of bias potential is 0V, halogen light light source is from electrolytic cell from left to right to acetyl chloride sulphur
It is irradiated for choline electrolyte, the photoelectric current that measurement obtains the chlopyrifos solution of different known concentrations respectively inhibits signal value；
(4) using the concentration of chlopyrifos solution as abscissa, using the inhibition photo-signal value of chlopyrifos solution as ordinate,
It makes chlopyrifos concentration and inhibits the linear relationship chart of photoelectric current.
C, test sample Chlorpyrifos concentration:
(1) in clean conductive glass surface CH3NH3PbI3It after the modification of/CS/AChE suspension, is placed in 4 DEG C and dries, make
At MIP/ITO/CH3NH3PbI3/ CS/AChE electrode；
(2) it is extracted from vegetables and obtains chlopyrifos solution to be measured, by MIP/ITO/CH3NH3PbI3/ CS/AChE electrode immerses
It is taken out after 10min in test sample, insertion contains 0.6mmolL equipped with 10mL-1The phosphate-buffered of acetyl chloride thiocholine
In the electrolytic cell of solution, measurement chlopyrifos inhibits photoelectric current；
(3) with MIP/ITO/CH3NH3PbI3/ CS/AChE electrode is working electrode, and working electrode is immersed chlopyrifos to be measured
It is taken out after 10min after solution, to be saturated potassium chloride electrode as reference electrode, using platinum electrode as auxiliary electrode, by working electrode, ginseng
It is respectively put into than electrode and auxiliary electrode containing 0.6mmolL-1The electrolysis of the phosphate buffer solution of acetyl chloride thiocholine
Chi Zhong；Halogen light light source is set on the left of electrolytic cell；Under conditions of bias potential is 0V, halogen light light source is left from electrolytic cell
The lateral right side is irradiated electrolyte, and measurement obtains the inhibition photo-signal value of chlopyrifos solution to be measured；
(4) using the linear relationship chart of the chlopyrifos concentration of production and inhibition photoelectric current, to be measured poison with poison is obtained with measurement
The inhibition photo-signal value of tick solution, finds test sample Chlorpyrifos concentration.
Vegetable sample ethyl alcohol dissolution filter.
Halogen light light source is 250 watts.
The concentration of the chlopyrifos solution of difference known concentration described in step b (3) is at least three.
Electrolytic cell material is quartz.
As shown in figure 3, a kind of remaining device of the dead tick of detection vegetable poisoning, including electrochemical workstation 8, light source 7, electrolysis
Three electricity are made in working electrode 2, reference electrode 3 and auxiliary electrode 1 by pond 5, working electrode 2, reference electrode 3 and auxiliary electrode 1
Polar body system, working electrode CH3NH3PbI3The electro-conductive glass of/CS/AChE modification, reference electrode 3 are molten containing saturation potassium chloride
The calomel electrode of liquid 4, auxiliary electrode are platinum electrode；Working electrode, reference electrode and auxiliary electrode are set in electrolytic cell 5；Electrolysis
Light source 7 is set on the left of pond 5；Electrochemical workstation 8 uses the CHI760D electrochemical workstation of Shanghai Chen Hua Instrument Ltd.,
Including Survey Software and three electrode interfaces, electrode interface is separately connected working electrode 2, reference electrode 3 and auxiliary electrode 1.Electrification
Work station 8 is learned to be connected with computer 9.
Embodiment 1
By MIP/ITO/CH3NH3PbI3/ CS/AChE electrode various concentration chlopyrifos solution (0,0.5,1.0,
10.0nmol L-1) immerse 10min after, take out, then respectively insertion contain 0.6mmolL-1Acetyl chloride thiocholine
0.1mol L-1In pH 7.0PBS electrolytic cell, halogen light light source is set on the left of electrolytic cell；Under conditions of bias potential is 0V,
Halogen light light source is irradiated acetyl chloride thiocholine electrolyte from electrolytic cell from left to right, and measurement has obtained difference respectively
Know that the photoelectric current of the chlopyrifos solution of concentration inhibits signal value；Using the concentration of chlopyrifos solution as abscissa, with chlopyrifos solution
Inhibition photo-signal value be ordinate, as shown in Figure 1.From Fig. 1, it can be seen that the chlopyrifos solution of various concentration is corresponding
Different inhibition photo-signal values.
Embodiment 2
By ITO/CH3NH3PbI3/ CS/AChE electrode various concentration chlopyrifos solution (0,0.02,0.05,0.1,
0.2,0.4,0.6,0.8,1.0 and 2.0nmol L-1) immerse 10min after, take out, then respectively insertion contain 0.6mmolL-1
The 0.1mol L of acetyl chloride thiocholine-1In pH 7.0PBS electrolytic cell, halogen light light source is set on the left of electrolytic cell；Inclined
Current potential is set as under conditions of 0V, halogen light light source shines acetyl chloride thiocholine electrolyte from electrolytic cell from left to right
It penetrates, the photoelectric current that measurement obtains the chlopyrifos solution of different known concentrations respectively inhibits signal value；With the concentration of chlopyrifos solution
The linear pass of chlopyrifos concentration and electric current is obtained using the inhibition photo-signal value of chlopyrifos solution as ordinate for abscissa
System's figure, as shown in Fig. 2, linear equation I=5.43+14.91CChlopyrifos。
Embodiment 3
The dead tick of vegetable poisoning is measured using the sensor, vegetable sample pretreatment is as follows: weighing the vegetable of 5g grinding
Dish sample (wild cabbage, radish, green vegetables) sprays a certain concentration chlopyrifos standard solution, then by vegetable sample on vegetable sample
It is placed in glass plate, the vegetable sample of processing is taken out after 10h.10mL water, 15mL is added into the vegetable sample of every a processing
Ethyl alcohol sufficiently shakes up, and is centrifuged 10min, takes supernatant, be settled to 100m with the pH 7.0PBS solution (pH=7.0) of 0.1mol/L
Sample solution is made in L, carries out mark-on reclaims measurement.It the results are shown in Table 1, the rate of recovery is 95.0%~103.0%, shows this method
It is good to the measurement result of practical vegetable sample Chlorpyrifos.
The measurement result (n=6) of 1 vegetable sample Chlorpyrifos of table
Claims (10)
1. the preparation method of the double identification type chlopyrifos sensors of enzyme-molecular engram based on nano-perovskite material, characterized in that
The preparation method comprises the following steps:
(1) preparation of perovskite precursor liquid
By CH3NH3I crystal and PbCl2Half an hour is mixed in DMF according to molar ratio 4:1 to get the perovskite of brown is arrived
Precursor liquid；
(2)ITO/CH3NH3PbI3The preparation of the bis- identification type sensors of/CS/AChE
Sheet is aoxidized cigarette tin ITO electro-conductive glass by (2-1), is put into containing 2mol L-1In the aqueous isopropanol of KOH, boil
30min is cleaned up, is dried for standby in middle ultrasound in ultrapure water with ultrasonic wave；
(2-2)ITO/CH3NH3PbI3The preparation of/CS/AChE sensor:
(2-2-1)ITO/CH3NH3PbI3The preparation of electrode: perovskite precursor liquid is equably spin-coated on ITO electro-conductive glass, is obtained
To ITO/CH3NH3PbI3Electrode；
(2-2-2) molecular engram sensor (MIP) MIP/ITO/CH3NH3PbI3The preparation of/CS: by ITO/CH3NH3PbI3Electrode
It is put into chitosan stock solution, chitosan stock solution contains 1.0mmolL-1Chlopyrifos, it is heavy with constant potential under conditions of -1.5V
Area method polymerize 5min, makes electrode surface while having polymerize chlopyrifos and chitosan；ITO/CH is taken out after the completion of deposition3NH3PbI3/
CS electrode drips the glutaraldehyde of volumetric concentration 0.1% in ITO/CH3NH3PbI3/ CS electrode surface, uses distilled water flushing after drying
Fall excessive glutaraldehyde, then dry, continues this electrode being immersed in 0.1molL-1In Klorvess Liquid, swept using cyclic voltammetric
The mode retouched, template molecule elution is fallen, and the potential region during cyclic voltammetry scan is -1.2~0.5V, after the completion will be electric
Pole is taken out and is cleaned, and the electrode dried is exactly molecular engram sensor MIP/ITO/CH3NH3PbI3/ CS, surface there are
The recognition site of many chlopyrifos molecules；
CS/AChE hanging drop is coated onto clean molecular engram sensor MIP/ITO/CH by (2-2-3)3NH3PbI3On/CS electrode
And in drying, MIP/ITO/CH is obtained3NH3PbI3/ CS/AChE sensor.
2. the double identification type chlopyrifos sensors of enzyme-molecular engram according to claim 1 based on nano-perovskite material
Preparation method, characterized in that CH in the step (1)3NH3The preparation method of I crystal is: by methylamine CH3NH2, hydroiodic acid HI
It is mixed at room temperature with ethanol solution, 1h is stirred in nitrogen environment, evaporation obtains crystal, washed 3 times with dimethyl ether, then by crystal
It dries under vacuum conditions, obtains white CH3NH3I crystal；CH3NH2: HI: ethyl alcohol (v/v/v)=12.54:22.80:95.
3. the double identification type chlopyrifos sensors of enzyme-molecular engram according to claim 1 based on nano-perovskite material
Preparation method, characterized in that the preparation method of chitosan stock solution in the step (2-2-2): by chitosan and glacial acetic acid
Mixing stands overnight and adds chlopyrifos after becoming uniformly to be configured to homogeneous solution.
4. the double identification type chlopyrifos sensors of enzyme-molecular engram according to claim 1 based on nano-perovskite material
Preparation method, characterized in that in the step (2-2-3) the circle number of cyclic voltammetry scan be 50 circle.
5. the double identification type chlopyrifos sensors of enzyme-molecular engram according to claim 1 based on nano-perovskite material
Preparation method, characterized in that the preparation method of CS/AChE suspension in the step (2-2-3): Chitosan powder is dissolved
In acetic acid solution, 5g/L chitosan solution is obtained；5g/L chitosan CS solution, adds 10.0mg acetylcholinesterase
AChE is gently mixed 15min at room temperature.
6. detecting the remaining method of the dead tick of vegetable poisoning using sensor described in claim 1, which is characterized in that the detection
Method the following steps are included:
A, the linear relationship chart of chlopyrifos concentration and electric current is made:
(a-1) with MIP/ITO/CH3NH3PbI3/ CS/AChE sensor is working electrode, to be saturated potassium chloride electrode as reference electricity
Pole is added 10mL in electrolytic cell and contains 0.6mmolL using platinum electrode as auxiliary electrode-1The phosphoric acid of acetyl chloride thiocholine
Salt buffer solution；Reference electrode and auxiliary electrode are respectively put into electrolytic cell；By MIP/ITO/CH3NH3PbI3/ CS/AChE work
Make electrode and immerse respectively in various criterion concentration chlopyrifos to take out after 10min, then be inserted into electrolytic cell respectively, is in bias potential
Under conditions of 0V, halogen light light source is irradiated acetyl chloride thiocholine electrolyte from electrolytic cell from left to right, surveys respectively
The photoelectric current for measuring the chlopyrifos solution of different known concentrations inhibits signal value；
(a-2) using the concentration of chlopyrifos solution as abscissa, inhibit signal value as ordinate using the photoelectric current of chlopyrifos solution, system
Make chlopyrifos concentration and inhibits the linear relationship chart of photoelectric current；
B, test sample Chlorpyrifos concentration:
(b-1) with MIP/ITO/CH3NH3PbI3/ CS/AChE sensor is working electrode, to be saturated potassium chloride electrode as reference electricity
Pole is added 10mL in electrolytic cell and contains 0.6mmolL using platinum electrode as auxiliary electrode-1The phosphoric acid of acetyl chloride thiocholine
Salt buffer solution；Reference electrode and auxiliary electrode are respectively put into electrolytic cell；It is molten to obtain chlopyrifos to be measured for extraction from vegetables
Liquid, by MIP/ITO/CH3NH3PbI3/ CS/AChE working electrode immerses in chlopyrifos solution to be measured to be taken out after 10min, insertion electricity
Xie Chizhong, under conditions of bias potential is 0V, halogen light light source is to the right irradiated electrolyte from the left of electrolytic cell, surveys
Measure the inhibition photo-signal value of chlopyrifos solution to be measured；
(b-2) using the linear relationship chart of the chlopyrifos concentration of production and inhibition photoelectric current, chlopyrifos to be measured is obtained with measurement
The inhibition photo-signal value of solution, obtains chlopyrifos solution Chlorpyrifos concentration to be measured.
7. the remaining method of the dead tick of detection vegetable poisoning according to claim 6, which is characterized in that the vegetable sample is used
Ethyl alcohol dissolution filter.
8. the remaining method of the dead tick of detection vegetable poisoning according to claim 6, which is characterized in that the step (b-1)
Described in the concentration of chlopyrifos solution of various criterion concentration be at least three.
9. a kind of remaining device of the dead tick of detection vegetable poisoning, characterized in that described device include electrochemical workstation, light source,
Electrolytic cell, working electrode, reference electrode and auxiliary electrode；
Working electrode, reference electrode and auxiliary electrode form three-electrode system, working electrode CH3NH3PbI3/ CS/AChE modification
Electro-conductive glass, i.e. MIP/ITO/CH3NH3PbI3/ CS/AChE sensor, reference electrode are saturation potassium chloride electrode, auxiliary electricity
Extremely platinum electrode；
Working electrode, reference electrode and auxiliary electrode are set in electrolytic cell；
Light source is set on the left of electrolytic cell；
Electrochemical workstation includes three electrode interfaces, and three electrode interfaces are separately connected working electrode, reference electrode and auxiliary electrode.
10. a kind of remaining device of the dead tick of detection vegetable poisoning according to claim 9, characterized in that the light source is
Halogen light light source, halogen light light source are 250 watts；The electrolytic cell material is quartz.
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