CN109254047A - A kind of preparation method and application of chrysanthemum ester insecticide Electrochemiluminescsensor sensor - Google Patents
A kind of preparation method and application of chrysanthemum ester insecticide Electrochemiluminescsensor sensor Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of chrysanthemum ester insecticide Electrochemiluminescsensor sensor.Belong to Nano-function thin films and biosensory analysis technology field.The present invention is prepared for iron cobalt dual-metal oxidate nano chip arrays can disposably throw first on electrode, the method for using growth in situ using its big specific surface area, directly be prepared in succession on iron cobalt dual-metal oxidate nano chip arrays in succession poly-dopamine film and in-stiu coating luminol using chrysanthemum ester insecticide 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 chrysanthemum ester insecticide Electrochemiluminescsensor 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 biosensory analysis technology field.
Background technique
Chrysanthemum ester insecticide is a kind of -2 substituted furan derivative of 5- nitro, is once a kind of important anti-infectives.
Such drug mainly includes furazolidone, furantoin, nitrofurazone etc., is mainly used for treating urinary infection, enteric bacteria
Infection, skin trauma are infected and prevent poultry intestinal tract infectious disease as food additives.However, due to the heredity of furazolidone
Toxicity and carcinogenesis, U.S. Food and Drug Administrations (FDA) in 2005 and European drug administration (EMA) have forbidden it
It is used in human and animal.Also, there is heterocyclic nitro class compound cell mutation, animal carcinogenic toxicity to have caused and face
The great attention of bed.Therefore, quick, highly selective and Sensitive Detection chrysanthemum ester insecticide the method for one kind is developed to publilc health
It is extremely important, and have 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 chrysanthemum ester insecticide Electrochemiluminescsensor sensor, prepared Electrochemiluminescsensor sensor, preparation is simple,
Favorable reproducibility, stability are strong, can be used for quick, the Sensitive Detection of chrysanthemum ester insecticide.Based on this purpose, the present invention is first one
Secondary property, which can be thrown, is prepared for iron cobalt dual-metal oxidate nano chip arrays on electrode, use growth in situ using its big specific surface area
Method, be directly prepared for poly-dopamine film and in-stiu coating in succession on iron cobalt dual-metal oxidate nano chip arrays in succession
Luminol using chrysanthemum ester insecticide as the molecularly imprinted polymer of template molecule, after by template molecule elution, originally
The position of template molecule has become hole, the i.e. molecularly imprinted polymer of eluted template molecule, as a result, a kind of chrysanthemum ester insecticide
Electrochemiluminescsensor sensor just prepares completion.When being used to detect chrysanthemum ester insecticide, by chrysanthemum ester insecticide electricity
Chemiluminescence sensor is caused to be inserted into solution to be measured, the chrysanthemum ester insecticide in solution to be measured can be adsorbed onto the hole of NIP.To
The chrysanthemum ester insecticide concentration surveyed in solution is bigger, and it is more to be adsorbed onto chrysanthemum ester insecticide in the hole of NIP.When progress electroluminescentization
When learning luminous detection, it can be become with increasing for chrysanthemum ester insecticide in the hole of NIP is adsorbed by the current strength of electrode
Small, corresponding electrochemiluminescence signal can also become smaller therewith, thus reduced according to the light signal strength of electrogenerated chemiluminescence
Degree is capable of the concentration of chrysanthemum ester insecticide in qualitative, quantitative solution to be measured.
The technical solution adopted by the invention is as follows:
1. a kind of preparation method of chrysanthemum ester insecticide Electrochemiluminescsensor sensor, chrysanthemum ester insecticide electroluminescentization
Luminescence sensor is learned by growth in situ on iron cobalt dual-metal oxide nano-slice array electrode FeCoO-nanoarray without template point
What sub- molecularly imprinted polymer NIP was obtained；Described is free from template molecule without template molecule molecularly imprinted polymer NIP
Molecularly imprinted polymer；The molecularly imprinted polymer without containing template molecule is polymerize by molecular engram containing template molecule
What object MIP was obtained by eluted template molecule；The MIP of molecularly imprinted polymer containing template molecule is containing template molecule
Molecularly imprinted polymer；The template molecule is chrysanthemum ester insecticide；
2. the preparation side of the FeCoO-nanoarray of iron cobalt dual-metal oxide nano-slice array electrode described in technical solution 1
Method 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 Fe (NO is weighed3)3With Co (NO3)2Mixture and 3 ~ 9 mmol urea CO (NH2)2, it is put into
In 50 mL beakers, 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 at a temperature of 130 DEG C 9 ~ 12 hours, then, taking-up makes annealing treatment 1 ~ 3 hour at 300 ~ 400 DEG C after drying, and is prepared into
To iron cobalt dual-metal oxidate nano chip arrays presoma electrode；
(4) the iron cobalt dual-metal oxidate nano chip arrays presoma electrode insertion obtained step (3) contains dopamine and mistake
In the phosphate buffer solution PBS of amine sulfate, 20 ~ 40 DEG C at a temperature of reaction 4 ~ 6 hours after, take out and use deionized water
It embathes 2 ~ 4 times, iron cobalt dual-metal oxide nano-slice array electrode FeCoO-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 cobalt piece,
Pure silicon piece, conductive carbon cloth；Fe (the NO3)3With Co (NO3)2Mixture in the molar ratio of iron and cobalt be 1:1；
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 of molecularly imprinted polymer containing template molecule of FeCoO-nanoarray growth in situ described in technical solution 1
Preparation method include 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) FeCoO-nanoarray prepared in technical solution 2 is clipped on Stirring device, before being inserted into step (2)
It drives 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, simultaneously
1 ~ 3 mL of luminol solution and 1 mmol azo two of 1 mmol/L is added dropwise simultaneously into mixed solution with 1 ~ 20 drop/sec of speed
Isobutyronitrile AIBN carries out initiation polymerization, and the molecular engram containing template molecule that growth in situ is obtained on FeCoO-nanoarray is poly-
Close object MIP；
4. FeCoO-nanoarray growth in situ described in technical solution 1 without template molecule molecularly imprinted polymer NIP
Preparation step are as follows: by obtained in technical solution 3 on FeCoO-nanoarray growth in situ molecule containing template molecule print
Mark polymer MIP is immersed in eluant, eluent, and template molecule is carried out 5 ~ 20 min of elution at room temperature, then takes out, obtains
Without template molecule molecularly imprinted polymer NIP；The eluant, eluent is the mixed liquor of formic acid and methanol, wherein formic acid and methanol
Volume ratio is 9:(1 ~ 5)；
5. the preparation step of chrysanthemum ester insecticide Electrochemiluminescsensor sensor described in technical solution 1 are as follows: by technical solution
In 2 ~ 4 the obtained growth in situ on FeCoO-nanoarray without template molecule molecularly imprinted polymer NIP, use deionization
Water logging is washed 2 ~ 4 times, is dried at room temperature, and chrysanthemum ester insecticide Electrochemiluminescsensor sensor is obtained；
6. being answered using chrysanthemum ester insecticide Electrochemiluminescsensor sensor prepared by technical solution described in technical solution 1 ~ 5
For the detection of chrysanthemum ester insecticide, including following applying step:
(1) standard solution is prepared: preparing the chrysanthemum ester insecticide standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: being working electrode by chrysanthemum ester insecticide Electrochemiluminescsensor sensor, in inserting step (1)
The chrysanthemum ester insecticide standard solution of the various concentration of preparation takes out after hatching 10 min, is 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 chrysanthemum ester insecticide standard solution containing various concentration is denoted asA i, response light
The difference that signal strength reduces is ΔA = A 0-A i, ΔAWith the mass concentration of chrysanthemum ester insecticide standard solutionCBetween it is linear
Relationship draws ΔA?CWorking curve；The phosphate buffer solution PBS concentration is 10 mmol/L, pH value 7.4；Institute
Parameter setting when the double rank pulse voltammetries detection stated 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 chrysanthemum ester insecticide detection: replace the chrysanthemum ester insecticide standard in step (1) with sample to be tested
Solution 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 chrysanthemum ester insecticide in sample to be tested.
7. chrysanthemum ester insecticide described in technical solution 1 ~ 6 is one of following chrysanthemum ester insecticide: Permethrin, tetramethrin,
Cypermethrin, decis, esbiothrin.
Beneficial achievement of the invention
(1) chrysanthemum ester insecticide Electrochemiluminescsensor sensor preparation of the present invention is simple, easy to operate, realizes to sample
Quick, sensitive, the highly selective detection of product, and it is at low cost, it can be applied to portable inspectiont, there is market development prospect；
(2) growth in situ divides the present invention on iron cobalt dual-metal oxide nano-slice array electrode FeCoO-nanoarray for the first time
On the one hand sub- imprinted polymer can grow molecule more, more evenly using the big specific surface area of FeCoO-nanoarray and print
Mark polymer, and FeCoO-nanoarray has excellent electron transmission ability, to greatly improve detection sensitivity；Separately
On the one hand, FeCoO-nanoarray has electro catalytic activity to hydrogen peroxide, may not need and horseradish peroxidase is added
Luminol-stabilization of hydrogen peroxide electrogenerated chemiluminescence system, highly effective reaction is realized, so that prepared sensor is without considering
Biological enzyme deactivation prob so that the use and storage of sensor can more stable and condition it is loose, thus into one
While step reduces signal background, improves detection sensitivity, greatly reduces testing cost and reduce environmental pollution；
(3) present invention is combined using the big specific surface area of iron cobalt dual-metal oxidate nano chip arrays with dopamine, so that more
Bar amine is forming the same of sufficiently thin poly-dopamine film in iron cobalt dual-metal oxide nano-slice array surface in-situ polymerization
When, on uniform fold to iron cobalt dual-metal oxidate nano chip arrays, thus for more preferably polymerizable molecular traces in next step
Polymer carries out place mat；Later using poly-dopamine to the strong connection function for the amino being rich on molecularly imprinted polymer, then
It dexterously uses FeCoO-nanoarray as blender, immersion stirring is carried out in molecular engram precursor mixed solution, lead to
The rate of addition and polymeric reaction temperature of control mixing speed, initiators for polymerization are crossed, it is straight on the surface FeCoO-nanoarray
Connecing growth in situ can control the molecularly imprinted polymer of film thickness, on the one hand FeCoO-nanoarray securely be born
Molecularly imprinted polymer and luminol are carried, to significantly improve the stability and again of prepared Electrochemiluminescsensor sensor
Existing property；On the other hand molecularly imprinted polymer can be effectively controlled in the film forming thickness of electrode surface, solve and be unable to control point
Sub- blotting membrane is unable to control the technical problem so as to cause poor reproducibility in electrode surface film forming thickness；In addition, more due to this hair
Bright preparation method coats effective control of film forming thickness and the in situ quantitation of luminol, and can sufficiently improve molecular engram is
The sensitivity of the Electrochemiluminescsensor sensor on basis and detection limit have important scientific meaning and application value.
Specific embodiment
The preparation of 1 FeCoO-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 Fe (NO is weighed3)3With Co (NO3)2Mixture and 3 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 at a temperature of DEG C 12 hours, then, taking-up makes annealing treatment 3 hours at 300 DEG C after drying, and iron cobalt dual-metal is prepared
Oxidate nano chip arrays presoma electrode；
(4) the iron cobalt dual-metal oxidate nano chip arrays presoma electrode insertion obtained step (3) contains dopamine and mistake
In the phosphate buffer solution PBS of amine sulfate, 20 DEG C at a temperature of reaction 4 hours after, take out simultaneously embathe 2 with deionized water
It is secondary, iron cobalt dual-metal oxide nano-slice array electrode FeCoO-nanoarray is prepared；
The electrode therein that can disposably throw is nickel foam；Fe (the NO3)3With Co (NO3)2Mixture in iron and cobalt rub
You are than being 1:1；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
For 0.1 mol/L, pH value 7.2.
The preparation of 2 FeCoO-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 Fe (NO are weighed3)3With Co (NO3)2Mixture and 6 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, 110
It is reacted at a temperature of DEG C 11 hours, then, taking-up makes annealing treatment 2 hours at 350 DEG C after drying, and iron cobalt dual-metal is prepared
Oxidate nano chip arrays presoma electrode；
(4) the iron cobalt dual-metal oxidate nano chip arrays presoma electrode insertion obtained step (3) contains dopamine and mistake
In the phosphate buffer solution PBS of amine sulfate, 30 DEG C at a temperature of reaction 5 hours after, take out simultaneously embathe 3 with deionized water
It is secondary, iron cobalt dual-metal oxide nano-slice array electrode FeCoO-nanoarray is prepared；
The electrode therein that can disposably throw is pure copper sheet；Fe (the NO3)3With Co (NO3)2Mixture in iron and cobalt rub
You are than being 1:1；Dopamine concentration is 3.5 mg/mL, and the concentration of Ammonium Persulfate 98.5 is 6.2 mg/mL, phosphate buffer solution PBS's
Concentration is 0.1 mol/L, pH value 8.0.
The preparation of 3 FeCoO-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 Fe (NO are weighed3)3With Co (NO3)2Mixture and 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, 130
It is reacted at a temperature of DEG C 9 hours, then, taking-up makes annealing treatment 1 hour at 400 DEG C after drying, and iron cobalt dual-metal is prepared
Oxidate nano chip arrays presoma electrode；
(4) the iron cobalt dual-metal oxidate nano chip arrays presoma electrode insertion obtained step (3) contains dopamine and mistake
In the phosphate buffer solution PBS of amine sulfate, 40 DEG C at a temperature of reaction 6 hours after, take out simultaneously embathe 4 with deionized water
It is secondary, iron cobalt dual-metal oxide nano-slice array electrode FeCoO-nanoarray is prepared；
The electrode therein that can disposably throw is conductive carbon cloth；Fe (the NO3)3With Co (NO3)2Mixture in iron and cobalt
Molar ratio is 1:1；Dopamine concentration is 5 mg/mL, and the concentration of Ammonium Persulfate 98.5 is 8 mg/mL, and phosphate buffer solution PBS's is dense
Degree is 0.1 mol/L, pH value 8.5.
The preparation method of 4 chrysanthemum ester insecticide Electrochemiluminescsensor 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) FeCoO-nanoarray prepared in embodiment 1 is clipped on Stirring device, the forerunner being inserted into step (2)
In body 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/
1 mL of luminol solution and 1 mmol azodiisobutyronitrile AIBN of 1 mmol/L is added dropwise into mixed solution simultaneously for the speed of second
Initiation polymerization is carried out, the MIP of molecularly imprinted polymer containing template molecule of growth in situ is obtained on FeCoO-nanoarray；
(4) molecularly imprinted polymer containing template molecule of growth in situ on FeCoO-nanoarray for obtaining step (3)
MIP is immersed in eluant, eluent, and template molecule is carried out 5 min of elution at room temperature, is then taken out, no template molecule point is obtained
Sub- imprinted polymer NIP；Continue to be embathed 2 times with deionized water, dry at room temperature, obtains the electroluminescent chemistry hair of chrysanthemum ester insecticide
Optical sensor；
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 chrysanthemum ester insecticide Electrochemiluminescsensor 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) FeCoO-nanoarray prepared in technical solution 2 is clipped on Stirring device, before being inserted into step (2)
It drives 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/
2 mL of luminol solution and 1 mmol azodiisobutyronitrile AIBN of 1 mmol/L is added dropwise into mixed solution simultaneously for the speed of second
Initiation polymerization is carried out, the MIP of molecularly imprinted polymer containing template molecule of growth in situ is obtained on FeCoO-nanoarray；
(4) molecularly imprinted polymer containing template molecule of growth in situ on FeCoO-nanoarray for obtaining step (3)
MIP is immersed in eluant, eluent, and template molecule is carried out 10 min of elution at room temperature, then takes out, obtains no template molecule
Molecularly imprinted polymer NIP；Continue to be embathed 3 times with deionized water, dry at room temperature, obtains the electroluminescent chemistry of chrysanthemum ester insecticide
Luminescence sensor；
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 chrysanthemum ester insecticide Electrochemiluminescsensor 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) FeCoO-nanoarray prepared in technical solution 2 is clipped on Stirring device, before being inserted into step (2)
It drives 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/
3 mL of luminol solution and 1 mmol azodiisobutyronitrile AIBN of 1 mmol/L is added dropwise into mixed solution simultaneously for the speed of second
Initiation polymerization is carried out, the MIP of molecularly imprinted polymer containing template molecule of growth in situ is obtained on FeCoO-nanoarray；
(4) molecularly imprinted polymer containing template molecule of growth in situ on FeCoO-nanoarray for obtaining step (3)
MIP is immersed in eluant, eluent, and template molecule is carried out 20 min of elution at room temperature, then takes out, obtains no template molecule
Molecularly imprinted polymer NIP；Continue to be embathed 4 times with deionized water, dry at room temperature, obtains the electroluminescent chemistry of chrysanthemum ester insecticide
Luminescence sensor；
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 chrysanthemum ester insecticide Electrochemiluminescsensor sensor of 7 embodiment 1 ~ 6 of embodiment preparation, is killed applied to pyrethroids class
The detection of worm agent, steps are as follows:
(1) standard solution is prepared: preparing the chrysanthemum ester insecticide standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: being working electrode by chrysanthemum ester insecticide Electrochemiluminescsensor sensor, in inserting step (1)
The chrysanthemum ester insecticide standard solution of the various concentration of preparation takes out after hatching 10 min, is 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 chrysanthemum ester insecticide standard solution containing various concentration is denoted asA i, response light
The difference that signal strength reduces is ΔA = A 0-A i, ΔAWith the mass concentration of chrysanthemum ester insecticide standard solutionCBetween it is linear
Relationship draws ΔA?CWorking curve；The phosphate buffer solution PBS concentration is 10 mmol/L, pH value 7.4；Institute
Parameter setting when the double rank pulse voltammetries detection stated 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 chrysanthemum ester insecticide detection: replace the chrysanthemum ester insecticide standard in step (1) with sample to be tested
Solution 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 chrysanthemum ester insecticide in sample to be tested.
The chrysanthemum ester insecticide Electrochemiluminescsensor sensor of 8 embodiment 1 ~ 6 of embodiment preparation, according to embodiment 7
Detecting step is applied to the detection of different chrysanthemum ester insecticides, and the range of linearity and detection limit are shown in Table 1:
The detection technique index of 1 chrysanthemum ester insecticide of table
The detection of chrysanthemum ester insecticide in 9 water sample of embodiment
Certain water sample is accurately pipetted, the chrysanthemum ester insecticide standard solution of certain mass concentration is added, is killed so that pyrethroids class is not added
The water sample of worm agent is blank, carries out recovery testu, is passed with chrysanthemum ester insecticide electrogenerated chemiluminescence prepared by embodiment 1 ~ 6
Sensor is detected according to the step of embodiment 7, measures the rate of recovery of chrysanthemum ester insecticide in water sample, and testing result is shown in Table 2:
The testing result of chrysanthemum ester insecticide in 2 water sample of table
2 testing result of table it is found that the relative standard deviation (RSD) of result less than 3.5 %, average recovery rate is 98.6 ~
101.2%, show that the present invention can be used for the detections of a variety of chrysanthemum ester insecticides in water sample, the high sensitivity of method, high specificity,
As a result accurate and reliable.
Claims (7)
1. a kind of preparation method of chrysanthemum ester insecticide Electrochemiluminescsensor sensor, which is characterized in that the pyrethroids class is killed
Worm agent Electrochemiluminescsensor sensor is by situ raw on iron cobalt dual-metal oxide nano-slice array electrode FeCoO-nanoarray
What length was obtained without template molecule molecularly imprinted polymer NIP；Described has been free from without template molecule molecularly imprinted polymer NIP
The molecularly imprinted polymer of template molecule；The molecularly imprinted polymer without containing template molecule is by containing template molecule point
What sub- imprinted polymer MIP was obtained by eluted template molecule；The MIP of molecularly imprinted polymer containing template molecule be containing
The molecularly imprinted polymer of template molecule；The template molecule is chrysanthemum ester insecticide.
2. iron cobalt dual-metal oxide nano-slice array electrode FeCoO-nanoarray as described in claim 1, feature exist
In the preparation method of the FeCoO-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 Fe (NO is weighed3)3With Co (NO3)2Mixture and 3 ~ 9 mmol urea CO (NH2)2, it is put into
In 50 mL beakers, 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 at a temperature of 130 DEG C 9 ~ 12 hours, then, taking-up makes annealing treatment 1 ~ 3 hour at 300 ~ 400 DEG C after drying, and is prepared into
To iron cobalt dual-metal oxidate nano chip arrays presoma electrode；
(4) the iron cobalt dual-metal oxidate nano chip arrays presoma electrode insertion obtained step (3) contains dopamine and mistake
In the phosphate buffer solution PBS of amine sulfate, 20 ~ 40 DEG C at a temperature of reaction 4 ~ 6 hours after, take out and use deionized water
It embathes 2 ~ 4 times, iron cobalt dual-metal oxide nano-slice array electrode FeCoO-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 cobalt piece,
Pure silicon piece, conductive carbon cloth；Fe (the NO3)3With Co (NO3)2Mixture in the molar ratio of iron and cobalt be 1:1；
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 FeCoO-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) FeCoO-nanoarray is clipped on Stirring device, is inserted into the precursor mixed solution in step (2),
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 ~ 20 drop/sec of speed
1 ~ 3 mL of luminol solution and 1 mmol azodiisobutyronitrile AIBN that 1 mmol/L is added dropwise simultaneously into mixed solution are drawn
Hair polymerization, obtains the MIP of molecularly imprinted polymer containing template molecule of growth in situ on FeCoO-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: will be given birth in situ on FeCoO-nanoarray obtained in claim 3
The long MIP of molecularly imprinted polymer containing template molecule is immersed in eluant, eluent, and template molecule is carried out 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 of chrysanthemum ester insecticide Electrochemiluminescsensor sensor as described in claim 1 are as follows: by claim 2
In ~ 4 the obtained growth in situ on FeCoO-nanoarray without template molecule molecularly imprinted polymer NIP, use deionized water
It embathes 2 ~ 4 times, dries at room temperature, obtain chrysanthemum ester insecticide Electrochemiluminescsensor sensor.
6. being answered using chrysanthemum ester insecticide Electrochemiluminescsensor sensor prepared by preparation method described in claim 1 ~ 5
Detection for chrysanthemum ester insecticide, which is characterized in that the detecting step is as follows:
(1) standard solution is prepared: preparing the chrysanthemum ester insecticide standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: being working electrode by chrysanthemum ester insecticide Electrochemiluminescsensor sensor, in inserting step (1)
The chrysanthemum ester insecticide standard solution of the various concentration of preparation takes out after hatching 10 min, is 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 chrysanthemum ester insecticide standard solution containing various concentration is denoted asA i, response light
The difference that signal strength reduces is ΔA = A 0-A i, ΔAWith the mass concentration of chrysanthemum ester insecticide standard solutionCBetween it is linear
Relationship draws ΔA?CWorking curve；The phosphate buffer solution PBS concentration is 10 mmol/L, pH value 7.4；Institute
Parameter setting when the double rank pulse voltammetries detection stated 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 chrysanthemum ester insecticide detection: replace the chrysanthemum ester insecticide standard in step (1) with sample to be tested
Solution 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 chrysanthemum ester insecticide in sample to be tested.
7. the chrysanthemum ester insecticide as described in claim 1 ~ 6 is one of following chrysanthemum ester insecticide: Permethrin, tetramethrin, chlorine
Cyano chrysanthemate, decis, esbiothrin.
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