CN109307696A - A kind of preparation method and application for the molecular engram sensing electrode detecting organo-chlorine pesticide - Google Patents
A kind of preparation method and application for the molecular engram sensing electrode detecting organo-chlorine pesticide Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of molecular engram sensing electrode for detecting organo-chlorine pesticide.Belong to Nano-function thin films and biosensory analysis technology field.The present invention is prepared for iron cobalt dual-metal nitride nano chip arrays can disposably throw first on electrode, using its big specific surface area and to the high adsorption activity of amino, and the amido functional group of poly-dopamine, using the method for growth in situ, directly be prepared in succession on iron cobalt dual-metal nitride nano chip arrays in succession poly-dopamine film and in-stiu coating luminol using organo-chlorine pesticide 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, it is a kind of detect organo-chlorine pesticide molecular engram sensing electrode just prepare 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
Organo-chlorine pesticide is for preventing and treating the organic compound for containing organic chlorine element in the constituent of phytopathy, insect pest
Object.Organo-chlorine pesticide is mainly manifested in infringement nerve and parenchymatous organ to the toxicity of human body.Acute toxicity to people is mainly
Nerve center is stimulated, slow poisoning shows as loss of appetite, and weight loss also can produce small brain disorder, blood forming organ barrier sometimes
Hinder.Document report, some organo-chlorine pesticides have carcinogenicity to experimental animal.Poisoner has strong impulse symptom, main table
Be now headache, it is dizzy, furious it is congested, shed tears keep in dark place, cough, pharyngalgia, out of strength, perspiration, salivation, nausea, loss of appetite, insomnia with
And Head And Face cacesthesia etc., moderate intoxication person, there are also vomiting, abdominal pain, have aches in the limbs, twitch, is purple in addition to having with above-mentioned symptom
Dark purple, expiratory dyspnea, tachycardia etc.；Severe intoxication person in addition to above-mentioned symptom obviously aggravates, still have high fever, hidrosis, contraction of muscle,
Epilepsy seizure, stupor.It is even dead.Food containing Organochlorine Pesticide Residues causes cannot be neglected potential to human health
It threatens.Therefore, it is extremely important to publilc health to develop a kind of quick, highly selective and Sensitive Detection organo-chlorine pesticide method,
And there is 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 the electrogenerated chemiluminescence sensing electrode of detection organo-chlorine pesticide, prepared electrogenerated chemiluminescence sensing electrode,
It is strong to prepare simple, favorable reproducibility, stability, can be used for quick, the Sensitive Detection of organo-chlorine pesticide.Based on this purpose, the present invention
It is prepared for iron cobalt dual-metal nitride nano chip arrays on electrode can disposably throw first, utilizes its big specific surface area and right
The high adsorption activity of amino and the amido functional group of poly-dopamine, using the method for growth in situ, in succession in iron cobalt dual-metal
Directly be prepared for poly-dopamine film and in-stiu coating luminol in succession on nitride nano chip arrays is with organo-chlorine pesticide
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, a kind of molecular engram sensing electrode for detecting organo-chlorine pesticide is just made as a result,
It is standby to complete.When for organo-chlorine pesticide is detected when, will test organo-chlorine pesticide molecular engram sensing electrode insertion to
It surveys in solution, the organo-chlorine pesticide in solution to be measured can be adsorbed onto the hole of NIP.Organo-chlorine pesticide concentration in solution to be measured
It is bigger, organo-chlorine pesticide is adsorbed onto the hole of NIP mostly when carrying out electrochemiluminescdetection detection, it is strong by the electric current of electrode
Degree can become smaller with increasing for organo-chlorine pesticide in the hole of NIP is adsorbed onto, and corresponding electrochemiluminescence signal also can be with
Become smaller, being capable of having in qualitative, quantitative solution to be measured thus according to the degree that the light signal strength of electrogenerated chemiluminescence reduces
The concentration of machine chloro pesticide.
The technical solution adopted by the invention is as follows:
1. a kind of preparation method for the molecular engram sensing electrode for detecting organo-chlorine pesticide, the detection organo-chlorine pesticide
Molecular engram sensing electrode is by growth in situ on iron cobalt dual-metal nitride nano chip arrays electrode FeCoN-nanoarray without mould
Plate molecular imprinted polymer NIP is obtained；Described has been free from template point without template molecule molecularly imprinted polymer NIP
The molecularly imprinted polymer of son；The molecularly imprinted polymer without containing template molecule is by molecular engram containing template molecule
What polymer MIP was obtained by eluted template molecule；The MIP of molecularly imprinted polymer containing template molecule is containing template point
The molecularly imprinted polymer of son；The template molecule is organo-chlorine pesticide；
2. the preparation side of the chip arrays electrode of iron cobalt dual-metal nitride nano described in technical solution 1 FeCoN-nanoarray
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 Co (NO is weighed3)2With Fe (NO3)3Mixture 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 9 ~ 12 hours at a temperature of 130 DEG C, iron cobalt dual-metal layered hydroxide nano-chip arrays presoma electricity is prepared
Pole；
(4) 5 in the iron cobalt dual-metal layered hydroxide nano-chip arrays presoma electrode insertion ammonium hydroxide obtained step (3) ~
It is taken out after 30 seconds, under ammonia environment, after being heated to 340 ~ 400 DEG C and being kept for 4 ~ 8 hours, continuation is dropped naturally under ammonia environment
To room temperature, it is then inserted into the phosphate buffer solution PBS containing dopamine and Ammonium Persulfate 98.5, in 20 ~ 40 DEG C of temperature
After lower reaction 4 ~ 6 hours, takes out and embathed 2 ~ 4 times with deionized water, iron cobalt dual-metal nitride nano chip arrays are prepared
Electrode FeCoN-nanoarray；
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；Co (the NO3)2With Fe (NO3)3Mixture in the molar ratio of cobalt and iron 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 FeCoN-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) FeCoN-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 FeCoN-nanoarray is poly-
Close object MIP；
4. FeCoN-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 FeCoN-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. detecting the preparation step of the molecular engram sensing electrode of organo-chlorine pesticide described in technical solution 1 are as follows: by technical side
In case 2 ~ 4 the obtained growth in situ on FeCoN-nanoarray without template molecule molecularly imprinted polymer NIP, spend from
Sub- water logging is washed 2 ~ 4 times, is dried at room temperature, and the molecular engram sensing electrode of detection organo-chlorine pesticide is obtained；
6. using the molecular engram sensing electrode for detecting organo-chlorine pesticide prepared by technical solution described in technical solution 1 ~ 5,
Applied to the detection of organo-chlorine pesticide, including following applying step:
(1) standard solution is prepared: preparing the organo-chlorine pesticide standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: the molecular engram sensing electrode that will test organo-chlorine pesticide is working electrode, inserting step (1)
The organo-chlorine pesticide standard solution of the various concentration of middle 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 organo-chlorine 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 organo-chlorine 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 organo-chlorine pesticide detection: replace the organo-chlorine 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 organo-chlorine pesticide in sample to be tested；
7. organo-chlorine pesticide described in technical solution 1 ~ 6 is one of following organo-chlorine pesticide: double rubigan trichloroethanes
(DDT), hexachlorocyclohexanes (six six six), tetradiphon, dicofol, pentachloronitrobenzene, termil (hundred bacterium
Clearly), heptachlor indenes (heptachlor), octa-klor (Niran).
Beneficial achievement of the invention
(1) the molecular engram sensing electrode preparation of detection organo-chlorine pesticide of the present invention is simple, easy to operate, realizes pair
Quick, sensitive, the highly selective detection of sample, 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 nitride nano chip arrays electrode FeCoN-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 FeCoN-nanoarray and print
Mark polymer, and FeCoN-nanoarray has excellent electron transmission ability, to greatly improve detection sensitivity；Separately
On the one hand, FeCoN-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 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 iron cobalt dual-metal nitride nano chip arrays in situ Polymerization, is forming sufficiently thin gather
While dopamine film, on uniform fold to iron cobalt dual-metal nitride nano chip arrays, thus to be more more preferable in next step
Polymerizable molecular imprinted polymer carry out place mat；Later using poly-dopamine to the strong of the amino being rich on molecularly imprinted polymer
Absorption connection function, then dexterously use FeCoN-nanoarray as blender, in molecular engram precursor mixed solution
In carry out immersion stirring, by control mixing speed, initiators for polymerization rate of addition and polymeric reaction temperature,
The surface FeCoN-nanoarray direct in-situ grows the molecularly imprinted polymer that can control film thickness, on the one hand makes
FeCoN-nanoarray can securely supporting molecular imprinted polymer and luminol, to significantly improve prepared electrochemistry
The stability and reproducibility of sensor；On the other hand molecularly imprinted polymer can effectively be controlled in electrode surface into film thickness
Degree, solve be unable to control molecular engram film be unable to control in electrode surface film forming thickness it is difficult so as to cause the technology of poor reproducibility
Topic；It, can be in addition, more coated due to preparation method of the invention to effective control of film forming thickness and the in situ quantitation of luminol
The sensitivity and detection limit for sufficiently improving the electrochemical sensor based on molecular engram have important scientific meaning and application
Value.
Specific embodiment
The preparation of 1 FeCoN-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 Co (NO is weighed3)2With Fe (NO3)3Mixture 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 12 hours at a temperature of DEG C, iron cobalt dual-metal layered hydroxide nano-chip arrays presoma electrode is prepared；
(4) the iron cobalt dual-metal layered hydroxide nano-chip arrays presoma electrode insertion that step (3) obtains is contained into DOPA
In the phosphate buffer solution PBS of amine and Ammonium Persulfate 98.5,20 DEG C at a temperature of reaction 4 hours after, take out and use deionized water
It embathes 2 times, iron cobalt dual-metal nitride nano chip arrays electrode FeCoN-nanoarray is prepared；
The electrode therein that can disposably throw is nickel foam；Co (the NO3)2With Fe (NO3)3Mixture in cobalt and iron 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 FeCoN-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 Ni (NO are weighed3)2With 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 11 hours at a temperature of DEG C, iron cobalt dual-metal layered hydroxide nano-chip arrays presoma electrode is prepared；
(4) the iron cobalt dual-metal layered hydroxide nano-chip arrays presoma electrode insertion that step (3) obtains is contained into DOPA
In the phosphate buffer solution PBS of amine and Ammonium Persulfate 98.5,30 DEG C at a temperature of reaction 5 hours after, take out and use deionized water
It embathes 3 times, iron cobalt dual-metal nitride nano chip arrays electrode FeCoN-nanoarray is prepared；
The electrode therein that can disposably throw is pure copper sheet；Co (the NO3)2With Fe (NO3)3Mixture in cobalt and iron 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 FeCoN-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 Co (NO are weighed3)2With Fe (NO3)3Mixture 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 9 hours at a temperature of DEG C, iron cobalt dual-metal layered hydroxide nano-chip arrays presoma electrode is prepared；
(4) the iron cobalt dual-metal nitride 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 layered hydroxide nano-chip arrays electrode FeCoN-nanoarray is prepared；
The electrode therein that can disposably throw is conductive carbon cloth；Co (the NO3)2With Fe (NO3)3Mixture in cobalt and iron
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.
Embodiment 4 detects the preparation method of the molecular engram sensing electrode of organo-chlorine pesticide
(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) FeCoN-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 FeCoN-nanoarray；
(4) molecularly imprinted polymer containing template molecule of growth in situ on FeCoN-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 molecule print of detection organo-chlorine pesticide
Mark sensing electrode；
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.
Embodiment 5 detects the preparation method of the molecular engram sensing electrode of organo-chlorine pesticide
(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) FeCoN-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 FeCoN-nanoarray；
(4) molecularly imprinted polymer containing template molecule of growth in situ on FeCoN-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 molecule of detection organo-chlorine pesticide
Trace sensing electrode；
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.
Embodiment 6 detects the preparation method of the molecular engram sensing electrode of organo-chlorine pesticide
(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) FeCoN-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 FeCoN-nanoarray；
(4) molecularly imprinted polymer containing template molecule of growth in situ on FeCoN-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 molecule of detection organo-chlorine pesticide
Trace sensing electrode；
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 molecular engram sensing electrode of the detection organo-chlorine pesticide of 7 embodiment 1 ~ 6 of embodiment preparation, is applied to organochlorine
The detection of pesticide, steps are as follows:
(1) standard solution is prepared: preparing the organo-chlorine pesticide standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: the molecular engram sensing electrode that will test organo-chlorine pesticide is working electrode, inserting step (1)
The organo-chlorine pesticide standard solution of the various concentration of middle 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 organo-chlorine 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 organo-chlorine 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 organo-chlorine pesticide detection: replace the organo-chlorine 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 organo-chlorine pesticide in sample to be tested.
The molecular engram sensing electrode of the detection organo-chlorine pesticide of 8 embodiment 1 ~ 6 of embodiment preparation, according to embodiment 7
Detecting step be applied to different organo-chlorine pesticides detection, the range of linearity and detection limit be shown in Table 1:
The detection technique index of 1 organo-chlorine pesticide of table
The detection of organo-chlorine pesticide in 9 water sample of embodiment
Certain water sample is accurately pipetted, the organo-chlorine pesticide standard solution of certain mass concentration is added, organo-chlorine pesticide not to be added
Water sample be blank, carry out recovery testu, with embodiment 1 ~ 6 prepare detection organo-chlorine pesticide molecular engram sense electricity
Pole is detected according to the step of embodiment 7, measures the rate of recovery of organo-chlorine pesticide in water sample, and testing result is shown in Table 2:
The testing result of organo-chlorine pesticide in 2 water sample of table
For 2 testing result of table it is found that the relative standard deviation (RSD) of result is less than 3.5 %, average recovery rate is 98.0 ~ 102%,
Show that the present invention can be used for the detection of Organochlorine Pesticides in water sample, as a result the high sensitivity of method, high specificity accurately may be used
It leans on.
Claims (7)
1. a kind of preparation method for the molecular engram sensing electrode for detecting organo-chlorine pesticide, which is characterized in that the detection has
The molecular engram sensing electrode of machine chloro pesticide is by former on iron cobalt dual-metal nitride nano chip arrays electrode FeCoN-nanoarray
Position growth is obtained without template molecule molecularly imprinted polymer NIP；Described is not without template molecule molecularly imprinted polymer NIP
Molecularly imprinted polymer containing template molecule；The molecularly imprinted polymer without containing template molecule is by containing template point
What sub- molecularly imprinted polymer MIP was obtained by eluted template molecule；The MIP of molecularly imprinted polymer containing template molecule is
Molecularly imprinted polymer containing template molecule；The template molecule is organo-chlorine pesticide.
2. iron cobalt dual-metal nitride nano chip arrays electrode FeCoN-nanoarray as described in claim 1, feature exist
In the preparation method of the FeCoN-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 Co (NO is weighed3)2With Fe (NO3)3Mixture 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 9 ~ 12 hours at a temperature of 130 DEG C, iron cobalt dual-metal layered hydroxide nano-chip arrays presoma electricity is prepared
Pole；
(4) 5 in the iron cobalt dual-metal layered hydroxide nano-chip arrays presoma electrode insertion ammonium hydroxide obtained step (3) ~
It is taken out after 30 seconds, under ammonia environment, after being heated to 340 ~ 400 DEG C and being kept for 4 ~ 8 hours, continuation is dropped naturally under ammonia environment
To room temperature, it is then inserted into the phosphate buffer solution PBS containing dopamine and Ammonium Persulfate 98.5, in 20 ~ 40 DEG C of temperature
After lower reaction 4 ~ 6 hours, takes out and embathed 2 ~ 4 times with deionized water, iron cobalt dual-metal nitride nano chip arrays are prepared
Electrode FeCoN-nanoarray；
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；Co (the NO3)2With Fe (NO3)3Mixture in the molar ratio of cobalt and iron 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 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 FeCoN-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) FeCoN-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 FeCoN-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 FeCoN-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 the molecular engram sensing electrode of detection organo-chlorine pesticide as described in claim 1 are as follows: right
Ask in 2 ~ 4 the growth in situ obtained on FeCoN-nanoarray without template molecule molecularly imprinted polymer NIP, spend from
Sub- water logging is washed 2 ~ 4 times, is dried at room temperature, and the molecular engram sensing electrode of detection organo-chlorine pesticide is obtained.
6. using the molecular engram sensing electrode for detecting organo-chlorine pesticide prepared by preparation method described in claim 1 ~ 5,
Detection applied to organo-chlorine pesticide, which is characterized in that the detecting step is as follows:
(1) standard solution is prepared: preparing the organo-chlorine pesticide standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: the molecular engram sensing electrode that will test organo-chlorine pesticide is working electrode, inserting step (1)
The organo-chlorine pesticide standard solution of the various concentration of middle 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 organo-chlorine 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 organo-chlorine 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 organo-chlorine pesticide detection: replace the organo-chlorine 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 organo-chlorine pesticide in sample to be tested.
7. the organo-chlorine pesticide as described in claim 1 ~ 6 is one of following organo-chlorine pesticide: double rubigan trichloroethanes
(DDT), hexachlorocyclohexanes (six six six), tetradiphon, dicofol, pentachloronitrobenzene, termil (hundred bacterium
Clearly), heptachlor indenes (heptachlor), octa-klor (Niran).
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