CN109254045A - A kind of preparation method and application for the cobalt-based nitride sensor detecting praziquantel - Google Patents
A kind of preparation method and application for the cobalt-based nitride sensor detecting praziquantel Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of cobalt-based nitride sensor for detecting praziquantel.Belong to Nano-function thin films and chemical biosensor technical field.The present invention is prepared for cobalt nitride nano-chip arrays can disposably throw first on electrode, using its big specific surface area and to the high adsorption activity of amino, using the method for growth in situ, directly it is prepared for the poly-dopamine film containing electron mediator in succession and using praziquantel molecule as the molecularly imprinted polymer of template molecule on cobalt 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, it is a kind of detect praziquantel cobalt-based nitride sensor just prepare completion.
Description
Technical field
The present invention relates to a kind of preparation method and applications of electrochemical sensor.Belong to Nano-function thin films and chemistry
Biosensor technology field.
Background technique
Praziquantel (Praziquantel) is a kind of for the mankind and the anthelmintic of animal, specifically treats tapeworm and fluke.
However since it is more toxic, medication must in strict accordance with require using.Otherwise dizzy, headache, nausea, abdomen be may result in
Bitterly, diarrhea, it is out of strength, have aches in the limbs, serious person can occasionally induce psychiatric disorder or go out it is possible that the symptoms such as palpitaition, uncomfortable in chest
Existing hemorrhage of digestive tract.Animal need to can butcher listing at withdrawal time 5 ~ 7 days or more.Remain such anthelmintic when people are edible
After animal food, drug toxicity can also be transferred to the mankind, to endanger human health.Currently, detection praziquantel molecule
Method mainly has enzyme-linked immunization, high performance liquid chromatography, mass spectrography etc..Such method instrument is valuable, complicated for operation, assayer
Member just can be carried out detection after needing professional training.Therefore, it develops as early as possible a kind of quick, highly selective and Sensitive Detection praziquantel
Method is extremely important to publilc health, and has 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 the cobalt-based nitride sensor of praziquantel is detected, prepared electrochemical sensor prepares simple, reproducibility
Well, stability is strong, can be used for quick, the Sensitive Detection of praziquantel molecule.Based on this purpose, the present invention can disposably thrown first
Cobalt nitride nano-chip arrays are prepared on electrode, using its big specific surface area and to the high adsorption activity of amino, using original position
The method of growth is directly prepared for the poly-dopamine film containing electron mediator in succession on cobalt nitride nano-chip arrays in succession
With using praziquantel molecule as the molecularly imprinted polymer of template molecule, after by template molecule elution, original template molecule
Position become hole, the i.e. molecularly imprinted polymer of eluted template molecule, as a result, it is a kind of detect praziquantel cobalt-based nitridation
Object sensor just prepares completion.When the cobalt-based nitride sensing for when detecting to praziquantel molecule, will test praziquantel
Device is inserted into solution to be measured, and the praziquantel molecule in solution to be measured can be adsorbed onto the hole of NIP.Praziquantel in solution to be measured
Molecular concentration is bigger, and it is more to be adsorbed onto praziquantel molecule in the hole of NIP.When carrying out Electrochemical Detection, the strong of electric current is detected
Degree can be with being adsorbed onto increasing and becoming smaller for praziquantel molecule in the hole of NIP, thus according to the degree that current strength reduces, energy
The concentration of praziquantel molecule in enough qualitative, quantitative solution to be measured.
The technical solution adopted by the invention is as follows:
1. a kind of preparation method for the cobalt-based nitride sensor for detecting praziquantel, the cobalt-based nitridation of the detection praziquantel
Object sensor is by growth in situ on cobalt nitride nano-chip arrays electrode CoN-nanoarray without template molecule molecularly imprinted polymer
What NIP was obtained；The molecularly imprinted polymer that template molecule is free from without template molecule molecularly imprinted polymer NIP；
The molecularly imprinted polymer without containing template molecule is by the MIP of molecularly imprinted polymer containing template molecule by elution mould
Plate molecule obtains；The MIP of molecularly imprinted polymer containing template molecule is the molecularly imprinted polymer containing template molecule；
The template molecule is praziquantel molecule；
2. the preparation method of cobalt nitride nano-chip arrays electrode CoN-nanoarray described in technical solution 1 includes following system
Standby step:
(1) it will can disposably throw electrode and carry out ultrasonic cleaning processing using dilute hydrochloric acid, dehydrated alcohol and deionization respectively, to go
Except the oxide layer and surface impurity that can disposably throw electrode；
(2) 1 ~ 3 mmol cabaltous nitrate hexahydrate Co (NO is weighed3)2·6H2O 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 hydroxide nano-chip arrays presoma electrode is prepared；
(4) the cobalt hydroxide nano-chip arrays presoma electrode that step (3) obtains is inserted into ammonium hydroxide and is taken out after 5 ~ 30 seconds, in ammonia
Under compression ring border, after being heated to 340 ~ 400 DEG C and being kept for 4 ~ 8 hours, continuation naturally rings to room temperature under ammonia environment, then by it
Be inserted into the phosphate buffer solution PBS containing dopamine, Ammonium Persulfate 98.5 and cobalt nitrate in, 20 ~ 40 DEG C at a temperature of reaction 4 ~
After 6 hours, takes out and embathed 2 ~ 4 times with deionized water, cobalt nitride nano-chip arrays electrode CoN-nanoarray is prepared；
The described disposable electrode of throwing is selected from one of cycle unit: foamed iron, foam copper, pure iron piece, pure copper sheet, pure iron piece,
Pure silicon piece, conductive carbon cloth；
In the phosphate buffer solution PBS containing dopamine, Ammonium Persulfate 98.5 and cobalt nitrate: dopamine concentration is 2 ~ 5
Mg/mL, the concentration of Ammonium Persulfate 98.5 are 3 ~ 8 mg/mL, and the concentration of 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's of molecularly imprinted polymer containing template molecule of CoN-nanoarray growth in situ described in technical solution 1
Preparation method includes following preparation step:
(1) 0.25 ~ 0.45mmol template molecule and 3 ~ 5 mmol 2- methacrylic acid MAA are weighed respectively in peace times bottle, are added
Enter 8 ~ 15 mL acetonitriles, 30 min of ultrasound to whole dissolutions；
(2) 15 ~ 25 mmol ethylene glycol dimethacrylate EDMA are added in the solution of step (1), 30 min of ultrasound
To being uniformly mixed, precursor mixed solution is obtained；
(3) CoN-nanoarray prepared in technical solution 2 is clipped on Stirring device, the forerunner being inserted into step (2)
In body mixed solution, in N2At a temperature of environment and 20 ~ 40 DEG C of water-bath, with 5 ~ 200 revolutions per seconds of speed Stirring, while with 1
~ 20 drops/sec of speed carries out initiation polymerization to 1 mmol azodiisobutyronitrile AIBN of mixed solution and dripping, in CoN-
The MIP of molecularly imprinted polymer containing template molecule of growth in situ is obtained on nanoarray；
4. CoN-nanoarray growth in situ described in technical solution 1 without template molecule molecularly imprinted polymer NIP's
Preparation step are as follows: by the molecular engram containing template molecule of growth in situ gathers on CoN-nanoarray obtained in technical solution 3
It closes object MIP to be immersed in eluant, eluent, template molecule is subjected to 5 ~ 20 min of elution at room temperature, is then taken out, no mould is obtained
Plate molecular imprinted polymer NIP；The eluant, eluent is the mixed liquor of formic acid and methanol, wherein the volume of formic acid and methanol
Than for 9:(1 ~ 5)；
5. described in technical solution 1 detect praziquantel cobalt-based nitride sensor preparation step are as follows: by technical solution 2 ~
In 4 the obtained growth in situ on CoN-nanoarray without template molecule molecularly imprinted polymer NIP, soaked with deionized water
It washes 2 ~ 4 times, dries at room temperature, obtain the cobalt-based nitride sensor of detection praziquantel；
6. using the cobalt-based nitride sensor for detecting praziquantel prepared by technical solution described in technical solution 1 ~ 5, application
In the detection of praziquantel molecule, including following applying step:
(1) standard solution is prepared: preparing the praziquantel molecular criteria solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: the cobalt-based nitride sensor that will test praziquantel is working electrode, and inserting step is matched in (1)
The praziquantel molecular criteria solution of the various concentration of system 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 praziquantel molecular criteria solution containing various concentration is denoted asI i, response
The difference that current strength reduces is ΔI = I 0-I i, ΔIWith the mass concentration of praziquantel molecular criteria solutionCBetween linear pass
Δ is drawn by systemI?CWorking curve；The phosphate buffer solution PBS concentration is 10 mmol/L, pH value 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 praziquantel molecule detection: replace the praziquantel molecular criteria 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 current strength reduces according to responseIAnd working curve,
Obtain the content of praziquantel molecule in sample to be tested.
Beneficial achievement of the invention
(1) the cobalt-based nitride sensor preparation of detection praziquantel of the present invention is simple, easy to operate, realizes to sample
Quick, sensitive, highly selective detection, and it is at low cost, can be applied to portable inspectiont, there is market development prospect；
(2) the growth in situ molecularly imprinted polymer on cobalt nitride nano-chip arrays electrode CoN-nanoarray for the first time of the invention,
On the one hand more, molecularly imprinted polymer more evenly can be grown using the big specific surface area of CoN-nanoarray, and
CoN-nanoarray has excellent electron transmission ability, to greatly improve detection sensitivity；On the other hand, the present invention will
When on dopamine in-situ polymerization to cobalt nitride nano-chip arrays, creative is doped into cobalt ions as electron mediator, is examining
Electrochemical response electric current is directly generated when survey, allows sensor straight in the buffer solution it is not necessary that other media substance is added
Capable detection is tapped into, to greatly reduce testing cost simultaneously while further decreasing signal background, improving detection sensitivity
It 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 nitride nano-chip arrays in situ Polymerization, is forming sufficiently thin poly-dopamine film
While, on uniform fold to cobalt nitride nano-chip arrays, thus for more preferably polymerizable molecular imprinted polymers in next step
Carry out place mat；Later using poly-dopamine to the strong absorption connection function for the amino being rich on molecularly imprinted polymer, then ingeniously
It uses CoN-nanoarray as blender wonderfully, immersion stirring is carried out in molecular engram precursor mixed solution, pass through control
The rate of addition and polymeric reaction temperature of mixing speed processed, initiators for polymerization, in the surface CoN-nanoarray direct in-situ
Growth can control the molecularly imprinted polymer of film thickness, print the secured supporting molecular of CoN-nanoarray
Mark polymer, to significantly improve the stability and reproducibility of prepared electrochemical sensor；On the other hand it can effectively control
Molecularly imprinted polymer processed solves in the film forming thickness of electrode surface and is unable to control molecular engram film in electrode surface into film thickness
Degree is unable to control the technical problem so as to cause poor reproducibility；In addition, more since preparation method of the invention is to film forming thickness
The effectively in-stiu coating of control and electron mediator, can sufficiently improve the sensitive of the electrochemical sensor based on molecular engram
Degree and detection limit have important scientific meaning and application value.
Specific embodiment
The preparation of 1 CoN-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 cabaltous nitrate hexahydrate Co (NO is weighed3)2·6H2O and 3 mmol urea CO (NH2)2, it is put into 50 mL
In beaker, 30 mL deionized waters are added and stir to clarify, are then transferred into 50 mL ptfe autoclaves；
(3) in the disposable solution thrown in the reaction kettle that electrode is put into step (2) for handling step (1) well, 100
It is reacted 12 hours at a temperature of DEG C, cobalt hydroxide nano-chip arrays presoma electrode is prepared；
(4) the cobalt hydroxide nano-chip arrays presoma electrode that step (3) obtains is inserted into ammonium hydroxide and is taken out after 5 seconds, in ammonia
Under environment, be heated to 340 DEG C and keep 8 hours after, continuation naturally ring to room temperature under ammonia environment, be then inserted into containing
In the phosphate buffer solution PBS of dopamine, Ammonium Persulfate 98.5 and cobalt nitrate, 20 DEG C at a temperature of reaction 4 hours after, take out
And embathed 2 times with deionized water, cobalt nitride nano-chip arrays electrode CoN-nanoarray is prepared；
The electrode therein that can disposably throw is foamed iron；Dopamine concentration is 2 mg/mL, and the concentration of Ammonium Persulfate 98.5 is 3 mg/mL,
The concentration of cobalt nitrate is 0.1 mg/mL, and the concentration of phosphate buffer solution PBS is 0.1 mol/L, pH value 7.2.
The preparation of 2 CoN-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 cabaltous nitrate hexahydrate Co (NO are weighed3)2·6H2O and 6 mmol urea CO (NH2)2, it is put into 50 mL
In beaker, 30 mL deionized waters are added and stir to clarify, are then transferred into 50 mL ptfe autoclaves；
(3) in the disposable solution thrown in the reaction kettle that electrode is put into step (2) for handling step (1) well, 110
It is reacted 11 hours at a temperature of DEG C, cobalt hydroxide nano-chip arrays presoma electrode is prepared；
(4) the cobalt hydroxide nano-chip arrays presoma electrode that step (3) obtains is inserted into ammonium hydroxide and is taken out after 15 seconds, in ammonia
Under environment, be heated to 370 DEG C and keep 6 hours after, continuation naturally ring to room temperature under ammonia environment, be then inserted into containing
In the phosphate buffer solution PBS of dopamine, Ammonium Persulfate 98.5 and cobalt nitrate, 30 DEG C at a temperature of reaction 5 hours after, take out
And embathed 3 times with deionized water, cobalt nitride nano-chip arrays electrode CoN-nanoarray is prepared；
The electrode therein that can disposably throw is pure copper sheet；Dopamine concentration is 3.5 mg/mL, and the concentration of Ammonium Persulfate 98.5 is 6.2
Mg/mL, the concentration of cobalt nitrate are 0.3 mg/mL, and the concentration of phosphate buffer solution PBS is 0.1 mol/L, pH value 8.0.
The preparation of 3 CoN-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 cabaltous nitrate hexahydrate Co (NO are weighed3)2·6H2O and 9 mmol urea CO (NH2)2, it is put into 50 mL
In beaker, 30 mL deionized waters are added and stir to clarify, are then transferred into 50 mL ptfe autoclaves；
(3) in the disposable solution thrown in the reaction kettle that electrode is put into step (2) for handling step (1) well, 130
It is reacted 9 hours at a temperature of DEG C, cobalt hydroxide nano-chip arrays presoma electrode is prepared；
(4) the cobalt hydroxide nano-chip arrays presoma electrode that step (3) obtains is inserted into ammonium hydroxide and is taken out after 30 seconds, in ammonia
Under environment, be heated to 400 DEG C and keep 4 hours after, continuation naturally ring to room temperature under ammonia environment, be then inserted into containing
In the phosphate buffer solution PBS of dopamine, Ammonium Persulfate 98.5 and cobalt nitrate, 40 DEG C at a temperature of reaction 6 hours after, take out
And embathed 4 times with deionized water, cobalt nitride nano-chip arrays electrode CoN-nanoarray is prepared；
The electrode therein that can disposably throw is conductive carbon cloth；Dopamine concentration is 5 mg/mL, and the concentration of Ammonium Persulfate 98.5 is 8 mg/
ML, the concentration of cobalt nitrate are 0.5 mg/mL, and the concentration of phosphate buffer solution PBS is 0.1 mol/L, pH value 8.5.
Embodiment 4 detects the preparation method of the cobalt-based nitride sensor of praziquantel
(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) CoN-nanoarray prepared in embodiment 1 is clipped on Stirring device, the presoma being inserted into step (2)
In mixed solution, in N2At a temperature of environment and 20 DEG C of water-bath, with 200 revolutions per seconds of speed Stirring, while with 1 drop/sec
Speed to 1 mmol azodiisobutyronitrile AIBN of mixed solution and dripping carry out initiation polymerization, on CoN-nanoarray
To the MIP of molecularly imprinted polymer containing template molecule of growth in situ；
(4) MIP of molecularly imprinted polymer containing template molecule of growth in situ on CoN-nanoarray for obtaining step (3)
It is immersed in eluant, eluent, template molecule is subjected to 5 min of elution at room temperature, then takes out, obtains no template molecule molecule
Imprinted polymer NIP；Continue to be embathed 2 times with deionized water, dry at room temperature, the cobalt-based nitride for obtaining detection praziquantel passes
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.
Embodiment 5 detects the preparation method of the cobalt-based nitride sensor of praziquantel
(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) CoN-nanoarray prepared in technical solution 2 is clipped on Stirring device, the forerunner being inserted into step (2)
In body mixed solution, in N2At a temperature of environment and 30 DEG C of water-bath, with 60 revolutions per seconds of speed Stirring, while with 10 drops/sec
Speed to 1 mmol azodiisobutyronitrile AIBN of mixed solution and dripping carry out initiation polymerization, on CoN-nanoarray
To the MIP of molecularly imprinted polymer containing template molecule of growth in situ；
(4) MIP of molecularly imprinted polymer containing template molecule of growth in situ on CoN-nanoarray for obtaining step (3)
It is immersed in eluant, eluent, template molecule is subjected to 10 min of elution at room temperature, then takes out, obtains no template molecule molecule
Imprinted polymer NIP；Continue to be embathed 3 times with deionized water, dry at room temperature, the cobalt-based nitride for obtaining detection praziquantel passes
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.
Embodiment 6 detects the preparation method of the cobalt-based nitride sensor of praziquantel
(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) CoN-nanoarray prepared in technical solution 2 is clipped on Stirring device, the forerunner being inserted into step (2)
In body mixed solution, in N2At a temperature of environment and 40 DEG C of water-bath, with 5 revolutions per seconds of speed Stirring, while with 20 drops/sec
Speed to 1 mmol azodiisobutyronitrile AIBN of mixed solution and dripping carry out initiation polymerization, on CoN-nanoarray
To the MIP of molecularly imprinted polymer containing template molecule of growth in situ；
(4) MIP of molecularly imprinted polymer containing template molecule of growth in situ on CoN-nanoarray for obtaining step (3)
It is immersed in eluant, eluent, template molecule is subjected to 20 min of elution at room temperature, then takes out, obtains no template molecule molecule
Imprinted polymer NIP；Continue to be embathed 4 times with deionized water, dry at room temperature, the cobalt-based nitride for obtaining detection praziquantel passes
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 cobalt-based nitride sensor of the detection praziquantel of 7 embodiment 1 ~ 6 of embodiment preparation, is applied to praziquantel molecule
Detection, steps are as follows:
(1) standard solution is prepared: preparing the praziquantel molecular criteria solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: the cobalt-based nitride sensor that will test praziquantel is working electrode, and inserting step is matched in (1)
The praziquantel standard solution of the various concentration of system 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 praziquantel molecular criteria solution containing various concentration is denoted asI i, response current strength reduction
Difference is ΔI = I 0-I i, ΔIWith the mass concentration of praziquantel standard solutionCBetween it is linear, draw ΔI?CWork
Curve；The PBS is the phosphate buffer solution of 10 mmol/L, and the pH value of the phosphate buffer solution is 7.4；Institute
Parameter setting when the DPV detection stated are as follows: range and direction are 0 ~ 1 V, and stride is 0.05 V, and the burst length is 0.05 s, are adopted
The sample time is 0.016 s, and the pulse period is 0.5 s；
(4) in sample to be tested praziquantel detection: the praziquantel 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 praziquantel in product.
The cobalt-based nitride sensor of the detection praziquantel of 8 embodiment 1 ~ 6 of embodiment preparation, according to the inspection of embodiment 7
The detection that step is applied to praziquantel is surveyed, the range of linearity is 0.0001 ~ 100 mmol/L, and detection is limited to 30 nmol/L.
The detection of praziquantel in 9 pig urine samples of embodiment
Pig urine samples are accurately pipetted, the praziquantel standard solution of certain mass concentration are added, the pig urine sample of praziquantel not to be added
Product are blank, carry out recovery testu, the cobalt-based nitride sensor for detecting praziquantel prepared with embodiment 1 ~ 6, according to
The step of embodiment 7, is detected, and the rate of recovery of praziquantel in pig urine samples is measured, and testing result is shown in Table 1:
The testing result of praziquantel in 1 pig urine samples of table
1 testing result of table it is found that the relative standard deviation (RSD) of result less than 3.2 %, average recovery rate is 98.0 ~
101.6%, show that the present invention can be used for the detection of praziquantel in pig urine, as a result the high sensitivity of method, high specificity accurately may be used
It leans on.
The detection of praziquantel in 10 sheep urine samples of embodiment
Certain sheep urine samples are accurately pipetted, the praziquantel standard solution of certain mass concentration are added, the sheep of praziquantel not to be added
Urine samples are blank, carry out recovery testu, the cobalt-based nitride sensor for detecting praziquantel prepared with embodiment 1 ~ 6,
It is detected according to the step of embodiment 7, measures the rate of recovery of praziquantel in sheep urine samples, testing result is shown in Table 2:
The testing result of praziquantel in 2 sheep urine samples of table
For 2 testing result of table it is found that the relative standard deviation (RSD) of result is less than 3.2 %, average recovery rate is 99.0 ~ 101%,
Show the present invention can be used for sheep urine in praziquantel detection, the high sensitivity of method, high specificity, as a result accurately and reliably.
Claims (6)
1. a kind of preparation method for the cobalt-based nitride sensor for detecting praziquantel, which is characterized in that the detection praziquantel
Cobalt-based nitride sensor by growth in situ on cobalt nitride nano-chip arrays electrode CoN-nanoarray without template molecule molecule
Imprinted polymer NIP is obtained；The molecule print that template molecule is free from without template molecule molecularly imprinted polymer NIP
Mark polymer；The molecularly imprinted polymer without containing template molecule is by the MIP of molecularly imprinted polymer containing template molecule
It is obtained by eluted template molecule；The MIP of molecularly imprinted polymer containing template molecule is the molecule containing template molecule
Imprinted polymer；The template molecule is praziquantel molecule.
2. cobalt nitride nano-chip arrays electrode CoN-nanoarray as described in claim 1 is it is characterized in that, the CoN-
The preparation method of nanoarray includes following preparation step:
(1) it will can disposably throw electrode and carry out ultrasonic cleaning processing using dilute hydrochloric acid, dehydrated alcohol and deionization respectively, to go
Except the oxide layer and surface impurity that can disposably throw electrode；
(2) 1 ~ 3 mmol cabaltous nitrate hexahydrate Co (NO is weighed3)2·6H2O and 3 ~ 9 mmol urea CO (NH2)2, it is put into 50
In mL beaker, 30 mL deionized waters are added and stir to clarify, are then transferred into 50 mL ptfe autoclaves；
(3) in the disposable solution thrown in the reaction kettle that electrode is put into step (2) for handling step (1) well, 100 ~
It is reacted 9 ~ 12 hours at a temperature of 130 DEG C, iron hydroxide nano-chip arrays presoma electrode is prepared；
(4) the cobalt hydroxide nano-chip arrays presoma electrode that step (3) obtains is inserted into ammonium hydroxide and is taken out after 5 ~ 30 seconds, in ammonia
Under compression ring border, after being heated to 340 ~ 400 DEG C and being kept for 4 ~ 8 hours, continuation naturally rings to room temperature under ammonia environment, then by it
Be inserted into the phosphate buffer solution PBS containing dopamine, Ammonium Persulfate 98.5 and cobalt nitrate in, 20 ~ 40 DEG C at a temperature of reaction 4 ~
After 6 hours, takes out and embathed 2 ~ 4 times with deionized water, cobalt nitride nano-chip arrays electrode CoN-nanoarray is prepared；
The described disposable electrode of throwing is selected from one of cycle unit: nickel foam, foam copper, pure nickel piece, pure copper sheet, pure iron piece,
Pure silicon piece, conductive carbon cloth；
In the phosphate buffer solution PBS containing dopamine, Ammonium Persulfate 98.5 and cobalt nitrate: dopamine concentration is 2 ~ 5
Mg/mL, the concentration of Ammonium Persulfate 98.5 are 3 ~ 8 mg/mL, and the concentration of 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 CoN-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) CoN-nanoarray is clipped on Stirring device, is inserted into the precursor mixed solution in step (2), in N2
At a temperature of environment and 20 ~ 40 DEG C of water-bath, with 5 ~ 200 revolutions per seconds of speed Stirring, while with 1 ~ 20 drop/sec of speed to
1 mmol azodiisobutyronitrile AIBN of mixed solution and dripping carries out initiation polymerization, and life in situ is obtained on CoN-nanoarray
The long MIP of molecularly imprinted polymer containing template molecule.
4. as described in claim 1 without template molecule molecularly imprinted polymer NIP, it is characterised in that the no template point
The preparation step of sub- molecularly imprinted polymer NIP are as follows: by obtained in claim 3 on CoN-nanoarray growth in situ
The MIP of molecularly imprinted polymer containing template molecule be immersed in eluant, eluent, template molecule is subjected to elution 5 ~ 20 at room temperature
Min then takes out, and obtains no template molecule molecularly imprinted polymer NIP；The eluant, eluent is the mixing of formic acid and methanol
Liquid, wherein the volume ratio of formic acid and methanol is 9:(1 ~ 5).
5. the preparation step of the cobalt-based nitride sensor as described in claim 1 based on detection praziquantel are as follows: right
Ask in 2 ~ 4 the growth in situ obtained on CoN-nanoarray without template molecule molecularly imprinted polymer NIP, use deionization
Water logging is washed 2 ~ 4 times, is dried at room temperature, and the cobalt-based nitride sensor of detection praziquantel is obtained.
6. using the cobalt-based nitride sensor based on detection praziquantel prepared by preparation method described in claim 1 ~ 5,
Detection applied to praziquantel, which is characterized in that the detecting step is as follows:
(1) standard solution is prepared: preparing the praziquantel standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: the cobalt-based nitride sensor that will test praziquantel is working electrode, and inserting step is matched in (1)
The praziquantel standard solution of the various concentration of system 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 praziquantel 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 praziquantel 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 praziquantel detection: the praziquantel 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 praziquantel in product.
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