CN109254054A - A kind of preparation method and application of the Spanon sensor based on cobalt-based nitride nano array - Google Patents
A kind of preparation method and application of the Spanon sensor based on cobalt-based nitride nano array Download PDFInfo
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- CN109254054A CN109254054A CN201811306711.6A CN201811306711A CN109254054A CN 109254054 A CN109254054 A CN 109254054A CN 201811306711 A CN201811306711 A CN 201811306711A CN 109254054 A CN109254054 A CN 109254054A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
Abstract
The invention discloses a kind of preparation methods of Spanon sensor based on cobalt-based nitride nano array.Belong to Nano-function thin films and biosensory analysis technology field.The present invention is prepared for cobalt nickel bimetal 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 it is prepared for the poly-dopamine film containing electron mediator in succession and using Spanon as the molecularly imprinted polymer of template molecule on cobalt nickel bimetal nitride nano chip arrays in succession, 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 Spanon sensor based on cobalt-based nitride nano array just prepares completion.
Description
Technical field
The present invention relates to a kind of preparation method and applications of electro-chemical analyzing sensor.Belong to Nano-function thin films with
Biosensory analysis technology field.
Background technique
Spanon is also known as ampicillin, is a kind of beta-lactam antibiotic, is semi-synthetic penbritin, can treat
Various bacteria infection.Indication includes respiratory tract infection, urethral infection, meningitis, salmonella infection disease and the internal membrane of heart
It is scorching.Since its is easy to use, low in cost, it is chiefly used in infectious diseases caused by treating chicken sensitive bacteria, such as Escherichia coli, sramana
Salmonella, Pasteurella, staphylococcus and streptococcal infection etc..On October 27th, 2017, the research of World Health Organization's international cancer
In the carcinogenic substance inventory that mechanism announces, ampicillin is in 3 class carcinogenic substance inventories.Therefore, it develops a kind of quick, highly selective
It is extremely important to publilc health with the method for Sensitive Detection Spanon, and have wide market application prospect.
Molecular imprinting electrochemical sensor has high specific selectivity, excellent stability, excellent reproducibility, wide inspection
Survey range and floor detection limit.Due to the sensor prepare simple, easy to detect, high sensitivity, it is at low cost the advantages that it is extensive
Applied to the fields such as chromatographic isolation, film point, Solid Phase Extraction, medicine controlled releasing, chemical sensitisation.Molecularly imprinted polymer (MIP), also referred to as
It, being capable of specific recognition and the specific target molecule of selective absorption (i.e. template molecule) for " plastics antibody ".Due to molecular engram
Technology has many advantages that, such as organic reagent corrosion resistance, good stability, heat-resisting quantity and preparation are simple.Therefore, in mistake
In several years gone, electroanalysis is caused based on the MIP electrochemical sensor (MIP-ECS) that MIP is combined with electrochemical sensor
The detection of the focus of chemical field, especially small molecule contaminants.However, having in the preparation process of traditional MIP-ECS
The elution of template molecule difficulty, the disadvantages of thickness of blotting membrane is difficult to control, reproducibility is poor, limit molecular engram film and passed in electrochemistry
Application in sensor.These problems, especially molecular engram film thickness are not easy to control to lead to electrochemical sensor sensitivity decrease
And molecular engram film easily falls off from electrode surface the technical problem for causing stability and reproducibility to reduce during elution, limit
The application of MIP_ECS has been made, therefore, has found new molecularly imprinted polymer synthetic method, new molecular engram film electrode is repaired
The combination method of decorations method and molecular engram film and base material, to solve the preparation of MIP-ECS and have using problem important
Research significance 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 Spanon sensor based on cobalt-based nitride nano array, prepared electrochemical sensing electrode, preparation letter
List, favorable reproducibility, stability are strong, can be used as quick, Sensitive Detection of the electrochemical sensor for Spanon.Based on this purpose,
The present invention is prepared for cobalt nickel bimetal nitride nano chip arrays can disposably throw first on electrode, utilize its big specific surface
Product and to the high adsorption activity of amino and the amido functional group of poly-dopamine, using the method for growth in situ, in succession in cobalt nickel
Directly it is prepared for the poly-dopamine film containing electron mediator and in succession on bimetallic nitride nano-chip arrays with Spanon
For the molecularly imprinted polymer of template molecule, after by template molecule elution, the position of template molecule originally has become sky
Cave, the i.e. molecularly imprinted polymer of eluted template molecule, a kind of Spanon based on cobalt-based nitride nano array senses as a result,
Device just prepares completion.When being used to detect Spanon, by the Spanon sensor based on cobalt-based nitride nano array
It is inserted into solution to be measured, the Spanon in solution to be measured can be adsorbed onto the hole of NIP.Spanon concentration in solution to be measured is got over
Greatly, it is more to be adsorbed onto Spanon in the hole of NIP.When carrying out Electrochemical Detection, the intensity for detecting electric current can be with being adsorbed onto
Increasing for Spanon in the hole of NIP and become smaller, thus according to current strength reduce degree, being capable of qualitative, quantitative solution to be measured
In Spanon concentration.
The technical solution adopted by the invention is as follows:
1. a kind of preparation method of the Spanon sensor based on cobalt-based nitride nano array, described to be nitrogenized based on cobalt-based
The Spanon sensor of object nano-array is by situ on cobalt nickel bimetal nitride nano chip arrays electrode CoNiN-nanoarray
What growth was obtained without template molecule molecularly imprinted polymer NIP；Described is free from without template molecule molecularly imprinted polymer NIP
There is the molecularly imprinted polymer of template molecule；The molecularly imprinted polymer without containing template molecule is by containing template molecule
What molecularly imprinted polymer MIP was obtained by eluted template molecule；The MIP of molecularly imprinted polymer containing template molecule is to contain
There is the molecularly imprinted polymer of template molecule；The template molecule is Spanon；
2. the preparation side of the chip arrays electrode of cobalt nickel bimetal nitride nano described in technical solution 1 CoNiN-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 Ni (NO is weighed3)2With 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 9 ~ 12 hours at a temperature of 130 DEG C, cobalt nickel bimetal layered hydroxide nano-chip arrays presoma electricity is prepared
Pole；
(4) 5 in the cobalt nickel bimetal 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, Ammonium Persulfate 98.5 and cobalt nitrate, 20 ~ 40
After being reacted 4 ~ 6 hours at a temperature of DEG C, takes out and embathed 2 ~ 4 times with deionized water, cobalt nickel bimetal nitride is prepared and receives
Rice chip arrays electrode CoNiN-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；Ni (the NO3)2With Co (NO3)2Mixture in the molar ratio of nickel 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 cobalt nitrate is 0.1 ~ 0.5 mg/mL, phosphate buffer solution PBS
Concentration be 0.1 mol/L, pH value be 7.2 ~ 8.5；
3. the MIP of molecularly imprinted polymer containing template molecule of CoNiN-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) CoNiN-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
Initiation polymerization is carried out to 1 mmol azodiisobutyronitrile AIBN of mixed solution and dripping with 1 ~ 20 drop/sec of speed, in CoNiN-
The MIP of molecularly imprinted polymer containing template molecule of growth in situ is obtained on nanoarray；
4. CoNiN-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 CoNiN-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 the Spanon sensor based on cobalt-based nitride nano array described in technical solution 1 are as follows: by skill
In art scheme 2 ~ 4 the obtained growth in situ on CoNiN-nanoarray without template molecule molecularly imprinted polymer NIP, use
Deionized water is embathed 2 ~ 4 times, is dried at room temperature, and the Spanon sensor based on cobalt-based nitride nano array is obtained；
6. being passed using the Spanon prepared by technical solution described in technical solution 1 ~ 5 based on cobalt-based nitride nano array
Sensor, applied to the detection of Spanon, including following applying step:
(1) standard solution is prepared: preparing the Spanon standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: will be working electrode, inserting step based on the Spanon sensor of cobalt-based nitride nano array
(1) the Spanon standard solution for the various concentration prepared in 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, connects electrochemical workstation, 15 mL is successively added in a cell
Phosphate buffer solution PBS；Pass through the current-responsive of the working electrode of Differential Pulse Voltammetry DPV detection assembling；Blank standard specimen
Response current intensity be denoted asI 0, the response current intensity of the Spanon standard solution containing various concentration is denoted asI i, response current
The difference of strength reduction is ΔI = I 0-I i, ΔIWith the mass concentration of Spanon standard solutionCBetween it is linear, draw
ΔI?CWorking curve；The phosphate buffer solution PBS concentration is 10 mmol/L, pH value 7.4；The DPV detection
When parameter setting are as follows: range and direction are 0 ~ 1 V, and stride is 0.05 V, and the burst length is 0.05 s, and the sampling time is
0.016 s, pulse period are 0.5 s；
(4) in sample to be tested Spanon detection: the Spanon standard solution in step (1) is replaced with sample to be tested, according to step
Suddenly the method in (2) and (3) is detected, the difference DELTA that current strength reduces according to responseIAnd working curve, it obtains to test sample
The content of Spanon in product.
Beneficial achievement of the invention
(1) the Spanon sensor preparation of the present invention based on cobalt-based nitride nano array is simple, easy to operate, realizes
Quick, sensitive, highly selective detection to sample, and it is at low cost, it can be applied to portable inspectiont, before there is market development
Scape；
(2) growth in situ divides the present invention on cobalt nickel bimetal nitride nano chip arrays electrode CoNiN-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 CoNiN-nanoarray and print
Mark polymer, and CoNiN-nanoarray has excellent electron transmission ability, to greatly improve detection sensitivity；Separately
On the one hand, when the present invention is by dopamine in-situ polymerization to cobalt nickel bimetal nitride nano chip arrays, creative is doped into
Cobalt ions directly generates electrochemical response electric current as electron mediator when detecting, allows sensor without being added
It is directly detected in the buffer solution of other media substance, thus further decreasing signal background, improving detection sensitivity
While, it greatly reduces testing cost and reduces 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 cobalt nickel bimetal nitride nano chip arrays in situ Polymerization, is forming sufficiently thin gather
While dopamine film, on uniform fold to cobalt nickel bimetal 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 CoNiN-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 CoNiN-nanoarray direct in-situ grows the molecularly imprinted polymer that can control film thickness, on the one hand makes
CoNiN-nanoarray can secured supporting molecular imprinted polymer, to significantly improve prepared electrochemical sensor
Stability and reproducibility；On the other hand molecularly imprinted polymer can be effectively controlled in the film forming thickness of electrode surface, solve
It is unable to control molecular engram film and is unable to control the technical problem so as to cause poor reproducibility in electrode surface film forming thickness；In addition,
More since preparation method of the invention is to the in-stiu coating of the effective control and electron mediator of film forming thickness, can sufficiently improve
The sensitivity of electrochemical sensor based on molecular engram and detection limit have important scientific meaning and application value.
Specific embodiment
The preparation of 1 CoNiN-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 Ni (NO is weighed3)2With 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 12 hours at a temperature of DEG C, cobalt nickel bimetal layered hydroxide nano-chip arrays presoma electrode is prepared；
(4) the cobalt nickel bimetal layered hydroxide nano-chip arrays presoma electrode insertion that step (3) obtains is contained into DOPA
In the phosphate buffer solution PBS of amine, Ammonium Persulfate 98.5 and cobalt nitrate, 20 DEG C at a temperature of reaction 4 hours after, taking-up be used in combination
Deionized water is embathed 2 times, and cobalt nickel bimetal nitride nano chip arrays electrode CoNiN-nanoarray is prepared；
The electrode therein that can disposably throw is nickel foam；Ni (the NO3)2With Co (NO3)2Mixture in nickel 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, and the concentration of cobalt nitrate is 0.1 mg/
The concentration of mL, phosphate buffer solution PBS are 0.1 mol/L, pH value 7.2.
The preparation of 2 CoNiN-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, cobalt nickel bimetal layered hydroxide nano-chip arrays presoma electrode is prepared；
(4) the cobalt nickel bimetal layered hydroxide nano-chip arrays presoma electrode insertion that step (3) obtains is contained into DOPA
In the phosphate buffer solution PBS of amine, Ammonium Persulfate 98.5 and cobalt nitrate, 30 DEG C at a temperature of reaction 5 hours after, taking-up be used in combination
Deionized water is embathed 3 times, and cobalt nickel bimetal nitride nano chip arrays electrode CoNiN-nanoarray is prepared；
The electrode therein that can disposably throw is pure copper sheet；Ni (the NO3)2With Co (NO3)2Mixture in nickel 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, and the concentration of cobalt nitrate is 0.3
The concentration of mg/mL, phosphate buffer solution PBS are 0.1 mol/L, pH value 8.0.
The preparation of 3 CoNiN-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 Ni (NO are weighed3)2With 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 9 hours at a temperature of DEG C, cobalt nickel bimetal layered hydroxide nano-chip arrays presoma electrode is prepared；
(4) the cobalt nickel bimetal nitride nano chip arrays presoma electrode insertion obtained step (3) contains dopamine, over cure
In the phosphate buffer solution PBS of acid amide and cobalt nitrate, 40 DEG C at a temperature of reaction 6 hours after, take out and use deionized water
It embathes 4 times, cobalt nickel bimetal layered hydroxide nano-chip arrays electrode CoNiN-nanoarray is prepared；
The electrode therein that can disposably throw is conductive carbon cloth；Ni (the NO3)2With Co (NO3)2Mixture in nickel 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 the concentration of cobalt nitrate is 0.5 mg/
The concentration of mL, phosphate buffer solution PBS are 0.1 mol/L, pH value 8.5.
The preparation method of Spanon sensor of the embodiment 4 based on cobalt-based nitride nano array
(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) CoNiN-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/
The speed of second carries out initiation polymerization to 1 mmol azodiisobutyronitrile AIBN of mixed solution and dripping, in CoNiN-nanoarray
On obtain the MIP of molecularly imprinted polymer containing template molecule of growth in situ；
(4) molecularly imprinted polymer containing template molecule of growth in situ on CoNiN-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 based on cobalt-based nitride nano array
Spanon 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 Spanon sensor of the embodiment 5 based on cobalt-based nitride nano array
(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) CoNiN-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/
The speed of second carries out initiation polymerization to 1 mmol azodiisobutyronitrile AIBN of mixed solution and dripping, in CoNiN-nanoarray
On obtain the MIP of molecularly imprinted polymer containing template molecule of growth in situ；
(4) molecularly imprinted polymer containing template molecule of growth in situ on CoNiN-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 based on cobalt-based nitride nano battle array
The Spanon sensor of column；
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 Spanon sensor of the embodiment 6 based on cobalt-based nitride nano array
(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) CoNiN-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/
The speed of second carries out initiation polymerization to 1 mmol azodiisobutyronitrile AIBN of mixed solution and dripping, in CoNiN-nanoarray
On obtain the MIP of molecularly imprinted polymer containing template molecule of growth in situ；
(4) molecularly imprinted polymer containing template molecule of growth in situ on CoNiN-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 based on cobalt-based nitride nano battle array
The Spanon sensor of column；
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 Spanon sensor based on cobalt-based nitride nano array of 7 embodiment 1 ~ 6 of embodiment preparation, applied to killing
The detection of worm amidine, steps are as follows:
(1) standard solution is prepared: preparing the Spanon standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: will be working electrode, inserting step based on the Spanon sensor of cobalt-based nitride nano array
(1) the Spanon standard solution for the various concentration prepared in 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, connects electrochemical workstation, 15 mL is successively added in a cell
PBS；Pass through the current-responsive of the working electrode of Differential Pulse Voltammetry DPV detection assembling；The response current intensity of blank standard specimen
It is denoted asI 0, the response current intensity of the Spanon standard solution containing various concentration is denoted asI i, the difference of response current strength reduction
For ΔI = I 0-I i, ΔIWith the mass concentration of Spanon standard solutionCBetween it is linear, draw ΔI?CWorking curve；
The PBS is the phosphate buffer solution of 10 mmol/L, and the pH value of the phosphate buffer solution is 7.4；Described
Parameter setting when DPV is detected are as follows: range and direction are 0 ~ 1 V, and stride is 0.05 V, and the burst length is 0.05 s, when sampling
Between be 0.016 s, the pulse period be 0.5 s；
(4) in sample to be tested Spanon detection: the Spanon standard solution in step (1) is replaced with sample to be tested, according to step
Suddenly the method in (2) and (3) is detected, the difference DELTA that current strength reduces according to responseIAnd working curve, it obtains to test sample
The content of Spanon in product.
The Spanon sensor based on cobalt-based nitride nano array of 8 embodiment 1 ~ 6 of embodiment preparation, according to implementation
The detecting step of example 7 is applied to the detection of Spanon, and the range of linearity is 0.0008 ~ 500 mmol/L, and detection is limited to 25 nmol/
L。
The detection of Spanon in 9 water sample of embodiment
Environmental water sample is accurately pipetted, the Spanon standard solution of certain mass concentration is added, is so that the water sample of Spanon not to be added
Blank, carry out recovery testu, with embodiment 1 ~ 6 prepare the Spanon sensor based on cobalt-based nitride nano array,
It is detected according to the step of embodiment 7, measures the rate of recovery of Spanon in water sample, testing result is shown in Table 1:
The testing result of Spanon in 1 water sample of table
1 testing result of table it is found that the relative standard deviation (RSD) of result less than 3.1 %, average recovery rate is 98.2 ~
99.6%, show that the present invention can be used for the detection of Spanon in water sample, as a result the high sensitivity of method, high specificity accurately may be used
It leans on.
Claims (6)
1. a kind of preparation method of the Spanon sensor based on cobalt-based nitride nano array, which is characterized in that the base
In cobalt-based nitride nano array Spanon sensor by cobalt nickel bimetal nitride nano chip arrays electrode CoNiN-
The upper growth in situ of nanoarray is obtained without template molecule molecularly imprinted polymer NIP；It is described without template molecule molecular engram
Polymer NIP is free from the molecularly imprinted polymer of template molecule；The molecular engram polymerization without containing template molecule
Object is to be obtained by the MIP of molecularly imprinted polymer containing template molecule by eluted template molecule；The molecule containing template molecule
Imprinted polymer MIP is the molecularly imprinted polymer containing template molecule；The template molecule is Spanon.
2. cobalt nickel bimetal nitride nano chip arrays electrode CoNiN-nanoarray as described in claim 1, feature exist
In the preparation method of the CoNiN-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 Ni (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, cobalt nickel bimetal layered hydroxide nano-chip arrays presoma electricity is prepared
Pole；
(4) 5 in the cobalt nickel bimetal 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, Ammonium Persulfate 98.5 and cobalt nitrate, 20 ~ 40
After being reacted 4 ~ 6 hours at a temperature of DEG C, takes out and embathed 2 ~ 4 times with deionized water, cobalt nickel bimetal nitride is prepared and receives
Rice chip arrays electrode CoNiN-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；Ni (the NO3)2With Fe (NO3)3Mixture in the molar ratio of nickel 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 cobalt nitrate is 0.1 ~ 0.5 mg/mL, phosphate buffer solution PBS
Concentration be 0.1 mol/L, pH value be 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 CoNiN-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) CoNiN-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
Initiation polymerization is carried out to 1 mmol azodiisobutyronitrile AIBN of mixed solution and dripping, original is obtained on CoNiN-nanoarray
The MIP of molecularly imprinted polymer containing template molecule of position growth.
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 CoNiN-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 Spanon sensor as described in claim 1 based on cobalt-based nitride nano array are as follows: will weigh
Benefit require in 2 ~ 4 the growth in situ obtained on CoNiN-nanoarray without template molecule molecularly imprinted polymer NIP, use
Deionized water is embathed 2 ~ 4 times, is dried at room temperature, and the Spanon sensor based on cobalt-based nitride nano array is obtained.
6. using the Spanon sensing prepared by preparation method described in claim 1 ~ 5 based on cobalt-based nitride nano array
Device, the detection applied to Spanon, which is characterized in that the detecting step is as follows:
(1) standard solution is prepared: preparing the Spanon standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: will be working electrode, inserting step based on the Spanon sensor of cobalt-based nitride nano array
(1) the Spanon standard solution for the various concentration prepared in 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, connects electrochemical workstation, 15 mL is successively added in a cell
Phosphate buffer solution PBS；Pass through the current-responsive of the working electrode of Differential Pulse Voltammetry DPV detection assembling；Blank standard specimen
Response current intensity be denoted asI 0, the response current intensity of the Spanon standard solution containing various concentration is denoted asI i, response current
The difference of strength reduction is ΔI = I 0-I i, ΔIWith the mass concentration of Spanon standard solutionCBetween it is linear, draw
ΔI?CWorking curve；The phosphate buffer solution PBS concentration is 10 mmol/L, pH value 7.4；The DPV inspection
Parameter setting when survey are as follows: range and direction are 0 ~ 1 V, and stride is 0.05 V, and the burst length is 0.05 s, and the sampling time is
0.016 s, pulse period are 0.5 s；
(4) in sample to be tested Spanon detection: the Spanon standard solution in step (1) is replaced with sample to be tested, according to step
Suddenly the method in (2) and (3) is detected, the difference DELTA that current strength reduces according to responseIAnd working curve, it obtains to test sample
The content of Spanon in product.
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