CN109254052A - A kind of preparation method and application of organophosphorus pesticide electrochemical luminescence sensor - Google Patents
A kind of preparation method and application of organophosphorus pesticide electrochemical luminescence sensor Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of organophosphorus pesticide electrochemical luminescence sensor.Belong to Nano-function thin films and biosensory analysis technology field.The present invention is prepared for nickel oxide nano-chip arrays can disposably throw first on electrode, using its big specific surface area and to the high adsorption activity of amino, using the method for growth in situ, directly be prepared in succession on nickel oxide nano-chip arrays in succession the poly-dopamine film containing electron mediator and in-stiu coating luminol using organophosphorus pesticide molecule as the molecularly imprinted polymer of template molecule, after by template molecule elution, the position of template molecule originally has become hole, that is the molecularly imprinted polymer of eluted template molecule, thus, a kind of organophosphorus pesticide electrochemical luminescence sensor just prepares completion.
Description
Technical field
The present invention relates to a kind of preparation method and applications of Electrochemiluminescsensor sensor.Belong to Nano-function thin films
With chemical biosensor technical field.
Background technique
Organophosphorus pesticide refers to the organic compound pesticide of phosphorus element-containing.It is mainly used for preventing and treating phytopathy, worm, crop smothering.Its
Being widely used in agricultural production, leads to that different degrees of residual occurs in crops.Harm of the organophosphorus pesticide to human body
Based on acute toxicity, after mostly occurring in large dosage or contacting repeatedly, it may appear that a series of neurotoxic symptoms, such as perspire,
It trembles, amentia, speech disorders, serious person will appear respiratory paralysis, or even dead.Currently, detection organophosphorus pesticide molecule
Method mainly have enzyme-linked immunization, high performance liquid chromatography, mass spectrography etc..Such method instrument is valuable, complicated for operation, chemical examination
Personnel just can be carried out detection after needing professional training.Therefore, it is organic phosphorus that a kind of quick, highly selective and Sensitive Detection is developed as early as possible
The method of pesticide is extremely important to publilc health, and has wide market application prospect.
Electroanalytical Chemistry sensor includes electrochemical sensor, Electrochemiluminescsensor sensor, optical electro-chemistry sensor etc.,
Such sensor has high specific selectivity, excellent stability, excellent reproducibility, wide detection range and floor detection
Limit.Due to the sensor prepare simple, easy to detect, high sensitivity, it is at low cost the advantages that be widely used in chromatographic isolation, film
Point, the fields such as Solid Phase Extraction, medicine controlled releasing, chemical sensitisation.Molecularly imprinted polymer (MIP), also referred to as " plastics antibody ", can
Specific recognition and the specific target molecule of selective absorption (i.e. template molecule).Since molecular imprinting technology has many advantages,
Such as organic reagent corrosion resistance, good stability, heat-resisting quantity and preparation are simple.Therefore, in the past few years, it is based on
The MIP Electroanalytical Chemistry sensor (MIP-ECS) that MIP is combined with Electroanalytical Chemistry sensor causes Electroanalytical Chemistry field
Focus, the especially detection of small molecule contaminants.However, having template point in the preparation process of traditional MIP-ECS
The disadvantages of sub- hardly possible elutes, the thickness of blotting membrane is difficult to control, reproducibility is poor, limits molecular engram film in Electroanalytical Chemistry sensor
In application.These problems, especially molecular engram film thickness are not easy to control cause electrochemical sensor sensitivity decrease and
Molecular engram film easily falls off from electrode surface during elution leads to the technical problem of stability and reproducibility reduction, limits
Therefore the application of MIP_ECS finds the modification side of new molecularly imprinted polymer synthetic method, new molecular engram film electrode
The combination method of method and molecular engram film and base material has important grind to solve preparation and the application problem of MIP-ECS
Study carefully meaning and market value.
Summary of the invention
The purpose of the present invention is to provide a kind of high specificity, prepare simple, easy to detect, high sensitivity, at low cost
The preparation method of organophosphorus pesticide electrochemical luminescence sensor, prepared Electrochemiluminescsensor sensor, preparation is simple, reappears
Property is good, stability is strong, can be used for quick, the Sensitive Detection of organophosphorus pesticide molecule.Based on this purpose, the present invention is first primary
Property, which can be thrown, is prepared for nickel oxide nano-chip arrays on electrode, using its big specific surface area and to the high adsorption activity of amino, adopt
With the method for growth in situ, it is directly prepared for the poly- DOPA containing electron mediator in succession on nickel oxide nano-chip arrays in succession
Amine film and in-stiu coating luminol using organophosphorus pesticide molecule as the molecularly imprinted polymer of template molecule, by template point
After son elution, the position of template molecule originally has become hole, the i.e. molecularly imprinted polymer of eluted template molecule, by
This, a kind of organophosphorus pesticide electrochemical luminescence sensor just prepares completion.When being used to detect organophosphorus pesticide molecule,
Organophosphorus pesticide electrochemical luminescence sensor is inserted into solution to be measured, the organophosphorus pesticide molecule in solution to be measured can be adsorbed onto
In the hole of NIP.Organophosphorus pesticide molecular concentration in solution to be measured is bigger, is adsorbed onto organophosphorus pesticide point in the hole of NIP
Son is more.It, can be organic in the hole of NIP with being adsorbed by the current strength of electrode when carrying out electrochemiluminescdetection detection
Phosphorus pesticide molecule increases and becomes smaller, and corresponding electrochemiluminescence signal can also become smaller therewith, to be sent out according to electroluminescent chemistry
The degree that the light signal strength of light reduces is capable of the concentration of organophosphorus pesticide molecule in qualitative, quantitative solution to be measured.
The technical solution adopted by the invention is as follows:
1. a kind of preparation method of organophosphorus pesticide electrochemical luminescence sensor, the organophosphorus pesticide electrochemical luminescence is passed
Sensor is by growth in situ on nickel oxide nano-chip arrays electrode NiN-nanoarray without template molecule molecularly imprinted polymer NIP
It obtains；The molecularly imprinted polymer that template molecule is free from without template molecule molecularly imprinted polymer NIP；It is described
The molecularly imprinted polymer without containing template molecule be by the MIP of molecularly imprinted polymer containing template molecule by eluted template point
What son obtained；The MIP of molecularly imprinted polymer containing template molecule is the molecularly imprinted polymer containing template molecule；It is described
Template molecule be organophosphorus pesticide molecule；
2. the preparation method of nickel oxide nano-chip arrays electrode NiN-nanoarray described in technical solution 1 includes following system
Standby step:
(1) it will can disposably throw electrode and carry out ultrasonic cleaning processing using dilute hydrochloric acid, dehydrated alcohol and deionization respectively, to go
Except the oxide layer and surface impurity that can disposably throw electrode；
(2) 1 ~ 3 mmol Nickelous nitrate hexahydrate Ni (NO is weighed3)2·6H2O and 3 ~ 9 mmol urea CO (NH2)2, it is put into 50
In mL beaker, 30 mL deionized waters are added and stir to clarify, are then transferred into 50 mL ptfe autoclaves；
(3) in the disposable solution thrown in the reaction kettle that electrode is put into step (2) for handling step (1) well, 100 ~
It is reacted 9 ~ 12 hours at a temperature of 130 DEG C, nickel hydroxide nano chip arrays presoma electrode is prepared；
(4) the nickel hydroxide nano chip arrays presoma electrode that step (3) obtains is inserted into ammonium hydroxide and is taken out after 5 ~ 30 seconds, in ammonia
Under compression ring border, after being heated to 340 ~ 400 DEG C and being kept for 4 ~ 8 hours, continuation naturally rings to room temperature under ammonia environment, then by it
Be inserted into the phosphate buffer solution PBS containing dopamine and Ammonium Persulfate 98.5 in, 20 ~ 40 DEG C at a temperature of react 4 ~ 6 hours
Afterwards, it takes out and is embathed 2 ~ 4 times with deionized water, nickel oxide nano-chip arrays electrode NiN-nanoarray is prepared；
The described disposable electrode of throwing is selected from one of cycle unit: nickel foam, foam copper, pure nickel piece, pure copper sheet, pure iron piece,
Pure silicon piece, conductive carbon cloth；
In the phosphate buffer solution PBS containing dopamine and Ammonium Persulfate 98.5: dopamine concentration is 2 ~ 5 mg/mL, mistake
The concentration of amine sulfate is 3 ~ 8 mg/mL, and the concentration of phosphate buffer solution PBS is 0.1 mol/L, and pH value is 7.2 ~ 8.5；
3. the MIP's of molecularly imprinted polymer containing template molecule of NiN-nanoarray growth in situ described in technical solution 1
Preparation method includes following preparation step:
(1) 0.25 ~ 0.45mmol template molecule and 3 ~ 5 mmol 2- methacrylic acid MAA are weighed respectively in peace times bottle, are added
Enter 8 ~ 15 mL acetonitriles, 30 min of ultrasound to whole dissolutions；
(2) 15 ~ 25 mmol ethylene glycol dimethacrylate EDMA are added in the solution of step (1), 30 min of ultrasound
To being uniformly mixed, precursor mixed solution is obtained；
(3) NiN-nanoarray prepared in technical solution 2 is clipped on Stirring device, the forerunner being inserted into step (2)
In body mixed solution, in N2At a temperature of environment and 20 ~ 40 DEG C of water-bath, with 5 ~ 200 revolutions per seconds of speed Stirring, while with 1
1 ~ 3 mL of luminol solution of 1 mmol/L of dropwise addition and 1 mmol azo two are different simultaneously into mixed solution for ~ 20 drops/sec of speed
Butyronitrile AIBN carries out initiation polymerization, and the molecularly imprinted polymer containing template molecule of growth in situ is obtained on NiN-nanoarray
MIP；
4. NiN-nanoarray growth in situ described in technical solution 1 without template molecule molecularly imprinted polymer NIP's
Preparation step are as follows: by the molecular engram containing template molecule of growth in situ gathers on NiN-nanoarray obtained in technical solution 3
It closes object MIP to be immersed in eluant, eluent, template molecule is subjected to 5 ~ 20 min of elution at room temperature, is then taken out, no mould is obtained
Plate molecular imprinted polymer NIP；The eluant, eluent is the mixed liquor of formic acid and methanol, wherein the volume of formic acid and methanol
Than for 9:(1 ~ 5)；
5. the preparation step of organophosphorus pesticide electrochemical luminescence sensor described in technical solution 1 are as follows: by technical solution 2 ~ 4
In the obtained growth in situ on NiN-nanoarray without template molecule molecularly imprinted polymer NIP, embathed with deionized water
It 2 ~ 4 times, dries at room temperature, obtains organophosphorus pesticide electrochemical luminescence sensor；
6. being applied to using organophosphorus pesticide electrochemical luminescence sensor prepared by technical solution described in technical solution 1 ~ 5
The detection of organophosphorus pesticide molecule, including following applying step:
(1) standard solution is prepared: the organophosphorus pesticide molecular criteria for preparing one group of various concentration including blank standard specimen is molten
Liquid；
(2) working electrode is modified: being working electrode by organophosphorus pesticide electrochemical luminescence sensor, is prepared in inserting step (1)
Various concentration organophosphorus pesticide molecular criteria solution, hatch 10 min after take out, embathed 3 times with deionized water；
(3) working curve is drawn: using saturated calomel electrode electrode as reference electrode, platinum electrode is used as to electrode, with step
(2) the working electrode composition three-electrode system modified, is connected in electrochemiluminescdetection detection equipment；In a cell first
Be added afterwards 15 mL phosphate buffer solution PBS and 1mL 2 mmol/L hydrogen peroxide (H2O2) solution；With double rank Pulse Voltammetries
Method applies cyclical voltage to the working electrode of assembling, detects the light signal strength of electrogenerated chemiluminescence；The response light of blank standard specimen
Signal strength is denoted asA 0, the response light signal strength of the organophosphorus pesticide standard solution containing various concentration is denoted asA i, response light letter
The difference of number strength reduction is ΔA = A 0-A i, ΔAWith the mass concentration of organophosphorus pesticide standard solutionCBetween linear pass
Δ is drawn by systemA?CWorking curve；The phosphate buffer solution PBS concentration is 10 mmol/L, pH value 7.4；It is described
The detection of double rank pulse voltammetries when parameter setting are as follows: initial potential is 0 V, and pulse potential is 0.9 V, and the burst length is
0.1 s, pulse period are 30 s；
(4) in sample to be tested organophosphorus pesticide detection: replace the organophosphorus pesticide standard in step (1) molten with sample to be tested
Liquid is detected according to the method in step (2) and (3), the difference DELTA that light signal strength reduces according to responseAIt is bent with work
Line obtains the content of organophosphorus pesticide in sample to be tested；
7. organophosphorus pesticide molecule described in technical solution 1 ~ 6 is one of following organophosphorus pesticide molecule: parathion, demeton,
Parathion-methyl, demeton-methyl, malathion, 2-dichloroethylk dimethyl phosphate, thiotep, metrifonate.
Beneficial achievement of the invention
(1) organophosphorus pesticide electrochemical luminescence sensor preparation of the present invention is simple, easy to operate, realizes to sample
Quickly, sensitive, highly selective detection, and it is at low cost, it can be applied to portable inspectiont, there is market development prospect；
(2) the growth in situ molecularly imprinted polymer on nickel oxide nano-chip arrays electrode NiN-nanoarray for the first time of the invention,
On the one hand more, molecularly imprinted polymer more evenly can be grown using the big specific surface area of NiN-nanoarray, and
NiN-nanoarray has excellent electron transmission ability, to greatly improve detection sensitivity；On the other hand, NiN-
Nanoarray has electro catalytic activity to hydrogen peroxide, and may not need addition horseradish peroxidase can be realized luminol-mistake
The stabilization of hydrogen oxide electrogenerated chemiluminescence system, highly effective reaction, so that prepared sensor is without considering that biological enzyme inactivation is asked
Topic, so that the use and storage of sensor can be more stable loose with condition, thus further decreasing signal back
While scape, raising detection sensitivity, greatly reduces testing cost and reduce environmental pollution；
(3) present invention specific surface area and dopamine big using high adsorption activity and nano-array electrode of the nitride to amino
It combines, so that dopamine in nickel oxide nano-chip arrays in situ Polymerization, is forming sufficiently thin poly-dopamine film
While, on uniform fold to nickel oxide nano-chip arrays, thus for more preferably polymerizable molecular imprinted polymers in next step
Carry out place mat；Later using poly-dopamine to the strong absorption connection function for the amino being rich on molecularly imprinted polymer, then ingeniously
It uses NiN-nanoarray as blender wonderfully, immersion stirring is carried out in molecular engram precursor mixed solution, pass through control
The rate of addition and polymeric reaction temperature of mixing speed processed, initiators for polymerization, in the surface NiN-nanoarray direct in-situ
Growth can control the molecularly imprinted polymer of film thickness, print the secured supporting molecular of NiN-nanoarray
Mark polymer and luminol, to significantly improve the stability and reproducibility of prepared Electrochemiluminescsensor sensor；Separately
On the one hand molecularly imprinted polymer can be effectively controlled in the film forming thickness of electrode surface, solve and be unable to control molecular engram film
The technical problem so as to cause poor reproducibility is unable to control in electrode surface film forming thickness；In addition, more due to preparation of the invention
Method is coated to effective control of film forming thickness and with the in situ quantitation of luminol, based on can sufficiently improving molecular engram
The sensitivity of Electrochemiluminescsensor sensor and detection limit have important scientific meaning and application value.
Specific embodiment
The preparation of 1 NiN-nanoarray of embodiment
(1) it will can disposably throw electrode and carry out ultrasonic cleaning processing using dilute hydrochloric acid, dehydrated alcohol and deionization respectively, to go
Except the oxide layer and surface impurity that can disposably throw electrode；
(2) 1 mmol Nickelous nitrate hexahydrate Ni (NO is weighed3)2·6H2O and 3 mmol urea CO (NH2)2, it is put into 50 mL
In beaker, 30 mL deionized waters are added and stir to clarify, are then transferred into 50 mL ptfe autoclaves；
(3) in the disposable solution thrown in the reaction kettle that electrode is put into step (2) for handling step (1) well, 100
It is reacted 12 hours at a temperature of DEG C, nickel hydroxide nano chip arrays presoma electrode is prepared；
(4) the nickel hydroxide nano chip arrays presoma electrode that step (3) obtains is inserted into ammonium hydroxide and is taken out after 5 seconds, in ammonia
Under environment, be heated to 340 DEG C and keep 8 hours after, continuation naturally ring to room temperature under ammonia environment, be then inserted into containing
In the phosphate buffer solution PBS of dopamine and Ammonium Persulfate 98.5,20 DEG C at a temperature of reaction 4 hours after, take out and spend from
Sub- water logging is washed 2 times, and nickel oxide nano-chip arrays electrode NiN-nanoarray is prepared；
The electrode therein that can disposably throw is nickel foam；Dopamine concentration is 2 mg/mL, and the concentration of Ammonium Persulfate 98.5 is 3 mg/mL,
The concentration of phosphate buffer solution PBS is 0.1 mol/L, pH value 7.2.
The preparation of 2 NiN-nanoarray of embodiment
(1) it will can disposably throw electrode and carry out ultrasonic cleaning processing using dilute hydrochloric acid, dehydrated alcohol and deionization respectively, to go
Except the oxide layer and surface impurity that can disposably throw electrode；
(2) 2 mmol Nickelous nitrate hexahydrate Ni (NO are weighed3)2·6H2O and 6 mmol urea CO (NH2)2, it is put into 50 mL
In beaker, 30 mL deionized waters are added and stir to clarify, are then transferred into 50 mL ptfe autoclaves；
(3) in the disposable solution thrown in the reaction kettle that electrode is put into step (2) for handling step (1) well, 110
It is reacted 11 hours at a temperature of DEG C, nickel hydroxide nano chip arrays presoma electrode is prepared；
(4) the nickel hydroxide nano chip arrays presoma electrode that step (3) obtains is inserted into ammonium hydroxide and is taken out after 15 seconds, in ammonia
Under environment, be heated to 370 DEG C and keep 6 hours after, continuation naturally ring to room temperature under ammonia environment, be then inserted into containing
In the phosphate buffer solution PBS of dopamine and Ammonium Persulfate 98.5,30 DEG C at a temperature of reaction 5 hours after, take out and spend from
Sub- water logging is washed 3 times, and nickel oxide nano-chip arrays electrode NiN-nanoarray is prepared；
The electrode therein that can disposably throw is pure copper sheet；Dopamine concentration is 3.5 mg/mL, and the concentration of Ammonium Persulfate 98.5 is 6.2
The concentration of mg/mL, phosphate buffer solution PBS are 0.1 mol/L, pH value 8.0.
The preparation of 3 NiN-nanoarray of embodiment
(1) it will can disposably throw electrode and carry out ultrasonic cleaning processing using dilute hydrochloric acid, dehydrated alcohol and deionization respectively, to go
Except the oxide layer and surface impurity that can disposably throw electrode；
(2) 3 mmol Nickelous nitrate hexahydrate Ni (NO are weighed3)2·6H2O and 9 mmol urea CO (NH2)2, it is put into 50 mL
In beaker, 30 mL deionized waters are added and stir to clarify, are then transferred into 50 mL ptfe autoclaves；
(3) in the disposable solution thrown in the reaction kettle that electrode is put into step (2) for handling step (1) well, 130
It is reacted 9 hours at a temperature of DEG C, nickel hydroxide nano chip arrays presoma electrode is prepared；
(4) the nickel hydroxide nano chip arrays presoma electrode that step (3) obtains is inserted into ammonium hydroxide and is taken out after 30 seconds, in ammonia
Under environment, be heated to 400 DEG C and keep 4 hours after, continuation naturally ring to room temperature under ammonia environment, be then inserted into containing
In the phosphate buffer solution PBS of dopamine and Ammonium Persulfate 98.5,40 DEG C at a temperature of reaction 6 hours after, take out and spend from
Sub- water logging is washed 4 times, and nickel oxide nano-chip arrays electrode NiN-nanoarray is prepared；
The electrode therein that can disposably throw is conductive carbon cloth；Dopamine concentration is 5 mg/mL, and the concentration of Ammonium Persulfate 98.5 is 8 mg/
The concentration of mL, phosphate buffer solution PBS are 0.1 mol/L, pH value 8.5.
The preparation method of 4 organophosphorus pesticide electrochemical luminescence sensor of embodiment
(1) 0.25 mmol template molecule and 3 mmol 2- methacrylic acid MAA are weighed respectively in peace times bottle, and 8 mL second are added
Nitrile, 30 min of ultrasound to whole dissolutions；
(2) 15 mmol ethylene glycol dimethacrylate EDMA are added in the solution of step (1), 30 min of ultrasound are to mixed
It closes uniformly, obtains precursor mixed solution；
(3) NiN-nanoarray prepared in embodiment 1 is clipped on Stirring device, the presoma being inserted into step (2)
In mixed solution, in N2At a temperature of environment and 20 DEG C of water-bath, with 200 revolutions per seconds of speed Stirring, while with 1 drop/sec
Speed into mixed solution simultaneously be added dropwise 1 mmol/L 1 mL of luminol solution and 1 mmol azodiisobutyronitrile AIBN into
Row causes polymerization, and the MIP of molecularly imprinted polymer containing template molecule of growth in situ is obtained on NiN-nanoarray；
(4) MIP of molecularly imprinted polymer containing template molecule of growth in situ on NiN-nanoarray for obtaining step (3)
It is immersed in eluant, eluent, template molecule is subjected to 5 min of elution at room temperature, then takes out, obtains no template molecule molecule
Imprinted polymer NIP；Continue to be embathed 2 times with deionized water, dry at room temperature, obtains organophosphorus pesticide electrochemical luminescence sensing
Device；
Eluant, eluent therein is the mixed liquor of formic acid and methanol, and wherein the volume ratio of formic acid and methanol is 9:1.
The preparation method of 5 organophosphorus pesticide electrochemical luminescence sensor of embodiment
(1) 0.35mmol template molecule and 4 mmol 2- methacrylic acid MAA are weighed respectively in peace times bottle, and 12 mL second are added
Nitrile, 30 min of ultrasound to whole dissolutions；
(2) 18 mmol ethylene glycol dimethacrylate EDMA are added in the solution of step (1), 30 min of ultrasound are to mixed
It closes uniformly, obtains precursor mixed solution；
(3) NiN-nanoarray prepared in technical solution 2 is clipped on Stirring device, the forerunner being inserted into step (2)
In body mixed solution, in N2At a temperature of environment and 30 DEG C of water-bath, with 60 revolutions per seconds of speed Stirring, while with 10 drops/sec
Speed into mixed solution simultaneously be added dropwise 1 mmol/L 2 mL of luminol solution and 1 mmol azodiisobutyronitrile AIBN into
Row causes polymerization, and the MIP of molecularly imprinted polymer containing template molecule of growth in situ is obtained on NiN-nanoarray；
(4) MIP of molecularly imprinted polymer containing template molecule of growth in situ on NiN-nanoarray for obtaining step (3)
It is immersed in eluant, eluent, template molecule is subjected to 10 min of elution at room temperature, then takes out, obtains no template molecule molecule
Imprinted polymer NIP；Continue to be embathed 3 times with deionized water, dry at room temperature, obtains organophosphorus pesticide electrochemical luminescence sensing
Device；
Eluant, eluent therein is the mixed liquor of formic acid and methanol, and wherein the volume ratio of formic acid and methanol is 9:3.
The preparation method of 6 organophosphorus pesticide electrochemical luminescence sensor of embodiment
(1) 0.45mmol template molecule and 5 mmol 2- methacrylic acid MAA are weighed respectively in peace times bottle, and 15 mL second are added
Nitrile, 30 min of ultrasound to whole dissolutions；
(2) 25 mmol ethylene glycol dimethacrylate EDMA are added in the solution of step (1), 30 min of ultrasound are to mixed
It closes uniformly, obtains precursor mixed solution；
(3) NiN-nanoarray prepared in technical solution 2 is clipped on Stirring device, the forerunner being inserted into step (2)
In body mixed solution, in N2At a temperature of environment and 40 DEG C of water-bath, with 5 revolutions per seconds of speed Stirring, while with 20 drops/sec
Speed into mixed solution simultaneously be added dropwise 1 mmol/L 3 mL of luminol solution and 1 mmol azodiisobutyronitrile AIBN into
Row causes polymerization, and the MIP of molecularly imprinted polymer containing template molecule of growth in situ is obtained on NiN-nanoarray；
(4) MIP of molecularly imprinted polymer containing template molecule of growth in situ on NiN-nanoarray for obtaining step (3)
It is immersed in eluant, eluent, template molecule is subjected to 20 min of elution at room temperature, then takes out, obtains no template molecule molecule
Imprinted polymer NIP；Continue to be embathed 4 times with deionized water, dry at room temperature, obtains organophosphorus pesticide electrochemical luminescence sensing
Device；
Eluant, eluent therein is the mixed liquor of formic acid and methanol, and wherein the volume ratio of formic acid and methanol is 9:5.
The organophosphorus pesticide sensor of 7 embodiment 1 ~ 6 of embodiment preparation, applied to the detection of organophosphorus pesticide, step
It is as follows:
(1) standard solution is prepared: preparing the organophosphorus pesticide standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: being working electrode by organophosphorus pesticide electrochemical luminescence sensor, is prepared in inserting step (1)
Various concentration organophosphorus pesticide standard solution, hatch 10 min after take out, embathed 3 times with deionized water；
(3) working curve is drawn: using saturated calomel electrode electrode as reference electrode, platinum electrode is used as to electrode, with step
(2) the working electrode composition three-electrode system modified, is connected in electrochemiluminescdetection detection equipment；In a cell first
Be added afterwards 15 mL phosphate buffer solution PBS and 1mL 2 mmol/L hydrogen peroxide (H2O2) solution；With double rank Pulse Voltammetries
Method applies cyclical voltage to the working electrode of assembling, detects the light signal strength of electrogenerated chemiluminescence；The response light of blank standard specimen
Signal strength is denoted asA 0, the response light signal strength of the organophosphorus pesticide standard solution containing various concentration is denoted asA i, response light letter
The difference of number strength reduction is ΔA = A 0-A i, ΔAWith the mass concentration of organophosphorus pesticide standard solutionCBetween linear pass
Δ is drawn by systemA?CWorking curve；The phosphate buffer solution PBS concentration is 10 mmol/L, pH value 7.4；It is described
The detection of double rank pulse voltammetries when parameter setting are as follows: initial potential is 0 V, and pulse potential is 0.9 V, and the burst length is
0.1 s, pulse period are 30 s；
(4) in sample to be tested organophosphorus pesticide detection: replace the organophosphorus pesticide standard in step (1) molten with sample to be tested
Liquid is detected according to the method in step (2) and (3), the difference DELTA that light signal strength reduces according to responseAIt is bent with work
Line obtains the content of organophosphorus pesticide in sample to be tested.
The organophosphorus pesticide sensor of 8 embodiment 1 ~ 6 of embodiment preparation, is applied to according to the detecting step of embodiment 7
The detection of different organophosphorus pesticides, the range of linearity and detection limit are shown in Table 1:
The detection technique index of 1 organophosphorus pesticide of table
The detection of 9 Organophosphorous in Water Samples pesticide of embodiment
Certain water sample is accurately pipetted, the organophosphorus pesticide standard solution of certain mass concentration is added, organophosphorus pesticide not to be added
The water sample of molecule is blank, carries out recovery testu, with organophosphorus pesticide sensor prepared by embodiment 1 ~ 6, according to implementation
The step of example 7, is detected, and the rate of recovery of Organophosphorous in Water Samples pesticide molecule is measured, and testing result is shown in Table 2:
The testing result of 2 Organophosphorous in Water Samples pesticide molecule of table
For 2 testing result of table it is found that the relative standard deviation (RSD) of result is less than 3.2 %, average recovery rate is 98.0 ~ 101%,
Show that the present invention can be used for the detection of Determination of Organophosphorus Pesticide molecule in water sample, the high sensitivity of method, high specificity are as a result quasi-
It is really reliable.
Claims (7)
1. a kind of preparation method of organophosphorus pesticide electrochemical luminescence sensor, which is characterized in that the organophosphorus pesticide electricity
Chemiluminescence sensor is by growth in situ on nickel oxide nano-chip arrays electrode NiN-nanoarray without template molecule molecular engram
Polymer NIP is obtained；The molecular engram for being free from template molecule without template molecule molecularly imprinted polymer NIP is poly-
Close object；The molecularly imprinted polymer without containing template molecule is passed through by the MIP of molecularly imprinted polymer containing template molecule
Eluted template molecule obtains；The MIP of molecularly imprinted polymer containing template molecule is the molecular engram containing template molecule
Polymer；The template molecule is organophosphorus pesticide molecule.
2. nickel oxide nano-chip arrays electrode NiN-nanoarray as described in claim 1 is it is characterized in that, the NiN-
The preparation method of nanoarray includes following preparation step:
(1) it will can disposably throw electrode and carry out ultrasonic cleaning processing using dilute hydrochloric acid, dehydrated alcohol and deionization respectively, to go
Except the oxide layer and surface impurity that can disposably throw electrode；
(2) 1 ~ 3 mmol Nickelous nitrate hexahydrate Ni (NO is weighed3)2·6H2O and 3 ~ 9 mmol urea CO (NH2)2, it is put into 50
In mL beaker, 30 mL deionized waters are added and stir to clarify, are then transferred into 50 mL ptfe autoclaves；
(3) in the disposable solution thrown in the reaction kettle that electrode is put into step (2) for handling step (1) well, 100 ~
It is reacted 9 ~ 12 hours at a temperature of 130 DEG C, nickel hydroxide nano chip arrays presoma electrode is prepared；
(4) the nickel hydroxide nano chip arrays presoma electrode that step (3) obtains is inserted into ammonium hydroxide and is taken out after 5 ~ 30 seconds, in ammonia
Under compression ring border, after being heated to 340 ~ 400 DEG C and being kept for 4 ~ 8 hours, continuation naturally rings to room temperature under ammonia environment, then by it
Be inserted into the phosphate buffer solution PBS containing dopamine and Ammonium Persulfate 98.5 in, 20 ~ 40 DEG C at a temperature of react 4 ~ 6 hours
Afterwards, it takes out and is embathed 2 ~ 4 times with deionized water, nickel oxide nano-chip arrays electrode NiN-nanoarray is prepared；
The described disposable electrode of throwing is selected from one of cycle unit: nickel foam, foam copper, pure nickel piece, pure copper sheet, pure iron piece,
Pure silicon piece, conductive carbon cloth；
In the phosphate buffer solution PBS containing dopamine, Ammonium Persulfate 98.5 and cobalt nitrate: dopamine concentration is 2 ~ 5
Mg/mL, the concentration of Ammonium Persulfate 98.5 are 3 ~ 8 mg/mL, and the concentration of phosphate buffer solution PBS is 0.1 mol/L, pH value is 7.2 ~
8.5。
3. the MIP of molecularly imprinted polymer containing template molecule as described in claim 1, which is characterized in that described containing template point
Sub- molecularly imprinted polymer MIP is that direct in-situ is grown on NiN-nanoarray, and preparation method includes following preparation step
It is rapid:
(1) 0.25 ~ 0.45mmol template molecule and 3 ~ 5 mmol 2- methacrylic acid MAA are weighed respectively in peace times bottle, are added
Enter 8 ~ 15 mL acetonitriles, 30 min of ultrasound to whole dissolutions；
(2) 15 ~ 25 mmol ethylene glycol dimethacrylate EDMA are added in the solution of step (1), 30 min of ultrasound
To being uniformly mixed, precursor mixed solution is obtained；
(3) NiN-nanoarray is clipped on Stirring device, is inserted into the precursor mixed solution in step (2), in N2
At a temperature of environment and 20 ~ 40 DEG C of water-bath, with 5 ~ 200 revolutions per seconds of speed Stirring, while with 1 ~ 20 drop/sec of speed to
1 ~ 3 mL of luminol solution and 1 mmol azodiisobutyronitrile AIBN that 1 mmol/L is added dropwise simultaneously in mixed solution are caused
Polymerization, obtains the MIP of molecularly imprinted polymer containing template molecule of growth in situ on NiN-nanoarray.
4. as described in claim 1 without template molecule molecularly imprinted polymer NIP, it is characterised in that the no template point
The preparation step of sub- molecularly imprinted polymer NIP are as follows: by obtained in claim 3 on NiN-nanoarray growth in situ
The MIP of molecularly imprinted polymer containing template molecule be immersed in eluant, eluent, template molecule is subjected to elution 5 ~ 20 at room temperature
Min then takes out, and obtains no template molecule molecularly imprinted polymer NIP；The eluant, eluent is the mixing of formic acid and methanol
Liquid, wherein the volume ratio of formic acid and methanol is 9:(1 ~ 5).
5. the preparation step as described in claim 1 based on organophosphorus pesticide electrochemical luminescence sensor are as follows: by claim 2
In ~ 4 the obtained growth in situ on NiN-nanoarray without template molecule molecularly imprinted polymer NIP, soaked with deionized water
It washes 2 ~ 4 times, dries at room temperature, obtain based on organophosphorus pesticide electrochemical luminescence sensor.
6. using, based on organophosphorus pesticide electrochemical luminescence sensor, being answered prepared by preparation method described in claim 1 ~ 5
Detection for organophosphorus pesticide, which is characterized in that the detecting step is as follows:
(1) standard solution is prepared: preparing the organophosphorus pesticide standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: being working electrode by organophosphorus pesticide electrochemical luminescence sensor, is prepared in inserting step (1)
Various concentration organophosphorus pesticide standard solution, hatch 10 min after take out, embathed 3 times with deionized water；
(3) working curve is drawn: using saturated calomel electrode electrode as reference electrode, platinum electrode is used as to electrode, with step
(2) the working electrode composition three-electrode system modified, is connected in electrochemiluminescdetection detection equipment；In a cell first
Be added afterwards 15 mL phosphate buffer solution PBS and 1mL 2 mmol/L hydrogen peroxide (H2O2) solution；With double rank Pulse Voltammetries
Method applies cyclical voltage to the working electrode of assembling, detects the light signal strength of electrogenerated chemiluminescence；The response light of blank standard specimen
Signal strength is denoted asA 0, the response light signal strength of the organophosphorus pesticide standard solution containing various concentration is denoted asA i, response light letter
The difference of number strength reduction is ΔA = A 0-A i, ΔAWith the mass concentration of organophosphorus pesticide standard solutionCBetween linear pass
Δ is drawn by systemA?CWorking curve；The phosphate buffer solution PBS concentration is 10 mmol/L, pH value 7.4；It is described
The detection of double rank pulse voltammetries when parameter setting are as follows: initial potential is 0 V, and pulse potential is 0.9 V, and the burst length is
0.1 s, pulse period are 30 s；
(4) in sample to be tested organophosphorus pesticide detection: replace the organophosphorus pesticide standard in step (1) molten with sample to be tested
Liquid is detected according to the method in step (2) and (3), the difference DELTA that light signal strength reduces according to responseAIt is bent with work
Line obtains the content of organophosphorus pesticide in sample to be tested.
7. the organophosphorus pesticide as described in claim 1 ~ 6 is one of following organophosphorus pesticide: parathion, demeton, methyl pair
Sulphur phosphorus, demeton-methyl, malathion, 2-dichloroethylk dimethyl phosphate, thiotep, metrifonate.
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