CN109254049A - A kind of preparation method and application of ampicillin sensor - Google Patents
A kind of preparation method and application of ampicillin sensor Download PDFInfo
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- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
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Abstract
The invention discloses a kind of preparation methods of ampicillin sensor.Belong to Nano-function thin films and biosensory analysis technology field.The present invention is prepared for ferronickel bimetallic stratiform hydroxide nano chip arrays can disposably throw first on electrode, utilize its big specific surface area and high activity hydroxy functional group, 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 ampicillin as the molecularly imprinted polymer of template molecule on ferronickel bimetallic stratiform hydroxide 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 ampicillin sensor 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
Ampicillin is also known as ampicillin, is a kind of beta-lactam antibiotic, is semi-synthetic penbritin, can control
Treat various bacteria infection.Indication includes respiratory tract infection, urethral infection, meningitis, salmonella infection disease and intracardiac
Film 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, sand
Door Salmonella, Pasteurella, staphylococcus and streptococcal infection etc..On October 27th, 2017, World Health Organization's international cancer is ground
In the carcinogenic substance inventory for studying carefully mechanism announcement, ampicillin is in 3 class carcinogenic substance inventories.Therefore, a kind of quick, high selection is developed
Property and the method for Sensitive Detection ampicillin are extremely important to publilc health, 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 ampicillin sensor, prepared electrochemical sensing electrode, preparation is simple, favorable reproducibility, stability are strong, can
Quick, the Sensitive Detection of ampicillin are used for as electrochemical sensor.Based on this purpose, the present invention can disposably thrown first
It is prepared for ferronickel bimetallic stratiform hydroxide nano chip arrays on electrode, utilizes its big specific surface area and high activity hydroxy
The amido functional group of functional group and poly-dopamine, using the method for growth in situ, in succession in ferronickel bimetallic stratiform hydroxide
The poly-dopamine film containing electron mediator is directly prepared on object nano-chip arrays in succession and using ampicillin as template point
The molecularly imprinted polymer of son, after by template molecule elution, the position of template molecule originally has become hole, that is, eluting
The molecularly imprinted polymer of template molecule, a kind of ampicillin sensor just prepares completion as a result,.When for ampicillin into
When row detection, ampicillin sensor is inserted into solution to be measured, the ampicillin in solution to be measured can be adsorbed onto the hole of NIP
In.Ampicillin concentration in solution to be measured is bigger, and it is more to be adsorbed onto ampicillin in the hole of NIP.When progress electrochemistry inspection
When survey, the intensity for detecting electric current can become smaller with increasing for ampicillin in the hole for being adsorbed onto NIP, thus strong according to electric current
Reduced degree is spent, the concentration of ampicillin in qualitative, quantitative solution to be measured is capable of.
The technical solution adopted by the invention is as follows:
1. a kind of preparation method of ampicillin sensor, the ampicillin sensor is by ferronickel bimetallic stratiform hydrogen-oxygen
Growth in situ is obtained without template molecule molecularly imprinted polymer NIP on compound nano-chip arrays electrode NiFe LDH-nanoarray
's；The molecularly imprinted polymer that template molecule is free from without template molecule molecularly imprinted polymer NIP；It is described not
Molecularly imprinted polymer containing template molecule is to be obtained by the MIP of molecularly imprinted polymer containing template molecule by eluted template molecule
It arrives；The MIP of molecularly imprinted polymer containing template molecule is the molecularly imprinted polymer containing template molecule；The mould
Plate molecule is ampicillin；
2. the hydroxide nano chip arrays electrode NiFe of ferronickel bimetallic stratiform described in technical solution 1 LDH-
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 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, ferronickel bimetallic stratiform hydroxide nano chip arrays presoma electricity is prepared
Pole；
(4) the ferronickel bimetallic stratiform 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 ~ 40 DEG C at a temperature of reaction 4 ~ 6 hours after, take out
And embathed 2 ~ 4 times with deionized water, ferronickel bimetallic stratiform hydroxide nano chip arrays electrode NiFe LDH- is prepared
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 iron 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 molecularly imprinted polymer containing template molecule of NiFe LDH-nanoarray growth in situ described in technical solution 1
The preparation method of MIP 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) the NiFe LDH-nanoarray prepared in technical solution 2 is clipped on Stirring device, is inserted into step (2)
Precursor mixed solution in, in N2At a temperature of environment and 20 ~ 40 DEG C of water-bath, with 5 ~ 200 revolutions per seconds of speed Stirring,
Initiation polymerization is carried out to 1 mmol azodiisobutyronitrile AIBN of mixed solution and dripping with 1 ~ 20 drop/sec of speed simultaneously,
The MIP of molecularly imprinted polymer containing template molecule of growth in situ is obtained on NiFe LDH-nanoarray；
4. NiFe LDH-nanoarray growth in situ described in technical solution 1 without template molecule molecularly imprinted polymer
The preparation step of NIP are as follows: by obtained in technical solution 3 on NiFe LDH-nanoarray growth in situ contain template molecule
Molecularly imprinted polymer MIP is immersed in eluant, eluent, and template molecule is carried out 5 ~ 20 min of elution at room temperature, is then taken out,
Obtain no template molecule molecularly imprinted polymer NIP；The eluant, eluent be formic acid and methanol mixed liquor, wherein formic acid with
The volume ratio of methanol is 9:(1 ~ 5)；
5. the preparation step of ampicillin sensor described in technical solution 1 are as follows: by technical solution 2 ~ 4 it is obtained
On NiFe LDH-nanoarray growth in situ without template molecule molecularly imprinted polymer NIP, embathe 2 ~ 4 with deionized water
It is secondary, it dries at room temperature, obtains ampicillin sensor；
6. using ampicillin sensor prepared by technical solution described in technical solution 1 ~ 5, the inspection applied to ampicillin
It surveys, including following applying step:
(1) standard solution is prepared: preparing the ampicillin standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: it is working electrode by ampicillin sensor, the various concentration prepared in inserting step (1)
Ampicillin standard solution 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 ampicillin standard solution containing various concentration is denoted asI i, response electricity
The difference that intensity of flow reduces is ΔI = I 0-I i, ΔIWith the mass concentration of ampicillin 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
Parameter setting when detection 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 ampicillin detection: replace the ampicillin standard solution in step (1) with sample to be tested, press
It is detected according to the method in step (2) and (3), the difference DELTA that current strength reduces according to responseIAnd working curve, obtain to
The content of ampicillin in sample.
Beneficial achievement of the invention
(1) sensor preparation in ampicillin of the present invention is simple, easy to operate, realizes to the quick, sensitive, high of sample
Selective enumeration method, and it is at low cost, it can be applied to portable inspectiont, there is market development prospect；
(2) present invention is former on ferronickel bimetallic stratiform hydroxide nano chip arrays electrode NiFe LDH-nanoarray for the first time
Position growth molecularly imprinted polymer, on the one hand can be grown more, more using the big specific surface area of NiFe LDH-nanoarray
Uniform molecularly imprinted polymer, and NiFe LDH-nanoarray has excellent electron transmission ability, to mention significantly
High detection sensitivity；On the other hand, the present invention is by dopamine in-situ polymerization to ferronickel bimetallic stratiform hydroxide nano piece battle array
When on column, creative is doped into cobalt ions as electron mediator, directly generates electrochemical response electric current when detecting, so that
Sensor can directly be detected in the buffer solution it is not necessary that other media substance is added, thus further decreasing signal
While background, raising detection sensitivity, greatly reduces testing cost and reduce environmental pollution；
(3) present invention is rich in using ferronickel bimetallic stratiform hydroxide nano chip arrays high activity hydroxy functional group and
Big specific surface area is combined with dopamine, so that dopamine is in ferronickel bimetallic stratiform hydroxide nano chip arrays surface original
When the polymerization of position, while forming sufficiently thin poly-dopamine film, uniform fold is received to ferronickel bimetallic layered hydroxide
On rice chip arrays, to carry out place mat for more preferably polymerizable molecular imprinted polymers in next step；Poly-dopamine is utilized later
Strong connection function to the amino being rich on hydroxy functional group and molecularly imprinted polymer, then dexterously use NiFe
LDH-nanoarray carries out immersion stirring as blender in molecular engram precursor mixed solution, passes through control stirring speed
The rate of addition and polymeric reaction temperature of degree, initiators for polymerization, it is raw in NiFe LDH-nanoarray surface direct in-situ
The long molecularly imprinted polymer that can control film thickness, on the one hand allows the secured supporting molecular of NiFe LDH-nanoarray
Imprinted polymer, to significantly improve the stability and reproducibility of prepared electrochemical sensor；It on the other hand can be effective
Molecularly imprinted polymer is controlled in the film forming thickness of electrode surface, solves and is unable to control molecular engram film in electrode surface film forming
The technical problem that thickness is unable to control so as to cause poor reproducibility；In addition, more since preparation method of the invention is to film forming thickness
Effective control and electron mediator in-stiu coating, can sufficiently improve the spirit of the electrochemical sensor based on molecular engram
Sensitivity and detection limit have important scientific meaning and application value.
Specific embodiment
The preparation of 1 NiFe LDH-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 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, ferronickel bimetallic stratiform hydroxide nano chip arrays presoma electrode is prepared；
(4) the ferronickel bimetallic stratiform 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 ferronickel bimetallic stratiform hydroxide nano chip arrays electrode NiFe LDH- is prepared
nanoarray；
The electrode therein that can disposably throw is nickel foam；Ni (the NO3)2With Fe (NO3)3Mixture in nickel 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, 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 NiFe LDH-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 Fe (NO3)3Mixture 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, ferronickel bimetallic stratiform hydroxide nano chip arrays presoma electrode is prepared；
(4) the ferronickel bimetallic stratiform 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 ferronickel bimetallic stratiform hydroxide nano chip arrays electrode NiFe LDH- is prepared
nanoarray；
The electrode therein that can disposably throw is pure copper sheet；Ni (the NO3)2With Fe (NO3)3Mixture in nickel 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, 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 NiFe LDH-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 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, ferronickel bimetallic stratiform hydroxide nano chip arrays presoma electrode is prepared；
(4) the ferronickel bimetallic stratiform 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, 40 DEG C at a temperature of reaction 6 hours after, taking-up be used in combination
Deionized water is embathed 4 times, and ferronickel bimetallic stratiform hydroxide nano chip arrays electrode NiFe LDH- is prepared
nanoarray；
The electrode therein that can disposably throw is conductive carbon cloth；Ni (the NO3)2With Fe (NO3)3Mixture in nickel 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 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 4 ampicillin sensor of embodiment
(1) 0.25 mmol template molecule and 3 mmol 2- methacrylic acid MAA are weighed respectively in peace times bottle, and 8 mL second are added
Nitrile, 30 min of ultrasound to whole dissolutions；
(2) 15 mmol ethylene glycol dimethacrylate EDMA are added in the solution of step (1), 30 min of ultrasound are to mixed
It closes uniformly, obtains precursor mixed solution；
(3) the NiFe LDH-nanoarray prepared in embodiment 1 is clipped on Stirring device, is inserted into step (2)
In precursor 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 carry out initiation polymerization to 1 mmol azodiisobutyronitrile AIBN of mixed solution and dripping, in NiFe LDH-
The MIP of molecularly imprinted polymer containing template molecule of growth in situ is obtained on nanoarray；
(4) molecular engram containing template molecule of growth in situ on NiFe LDH-nanoarray for obtaining step (3) polymerize
Object MIP is immersed in eluant, eluent, and template molecule is carried out 5 min of elution at room temperature, then takes out, obtains no template molecule
Molecularly imprinted polymer NIP；Continue to be embathed 2 times with deionized water, dries at room temperature, obtain ampicillin sensor；
Eluant, eluent therein is the mixed liquor of formic acid and methanol, and wherein the volume ratio of formic acid and methanol is 9:1.
The preparation method of 5 ampicillin sensor of embodiment
(1) 0.35mmol template molecule and 4 mmol 2- methacrylic acid MAA are weighed respectively in peace times bottle, and 12 mL second are added
Nitrile, 30 min of ultrasound to whole dissolutions；
(2) 18 mmol ethylene glycol dimethacrylate EDMA are added in the solution of step (1), 30 min of ultrasound are to mixed
It closes uniformly, obtains precursor mixed solution；
(3) the NiFe LDH-nanoarray prepared in technical solution 2 is clipped on Stirring device, is inserted into step (2)
Precursor mixed solution in, 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 of speed carries out initiation polymerization to 1 mmol azodiisobutyronitrile AIBN of mixed solution and dripping, in NiFe LDH-
The MIP of molecularly imprinted polymer containing template molecule of growth in situ is obtained on nanoarray；
(4) molecular engram containing template molecule of growth in situ on NiFe LDH-nanoarray for obtaining step (3) polymerize
Object MIP is immersed in eluant, eluent, and template molecule is carried out 10 min of elution at room temperature, is then taken out, no template point is obtained
Sub- molecularly imprinted polymer NIP；Continue to be embathed 3 times with deionized water, dries at room temperature, obtain ampicillin sensor；
Eluant, eluent therein is the mixed liquor of formic acid and methanol, and wherein the volume ratio of formic acid and methanol is 9:3.
The preparation method of 6 ampicillin sensor of embodiment
(1) 0.45mmol template molecule and 5 mmol 2- methacrylic acid MAA are weighed respectively in peace times bottle, and 15 mL second are added
Nitrile, 30 min of ultrasound to whole dissolutions；
(2) 25 mmol ethylene glycol dimethacrylate EDMA are added in the solution of step (1), 30 min of ultrasound are to mixed
It closes uniformly, obtains precursor mixed solution；
(3) the NiFe LDH-nanoarray prepared in technical solution 2 is clipped on Stirring device, is inserted into step (2)
Precursor mixed solution in, in N2At a temperature of environment and 40 DEG C of water-bath, with 5 revolutions per seconds of speed Stirring, while with 20
Drop/sec speed carry out initiation polymerization to 1 mmol azodiisobutyronitrile AIBN of mixed solution and dripping, in NiFe LDH-
The MIP of molecularly imprinted polymer containing template molecule of growth in situ is obtained on nanoarray；
(4) molecular engram containing template molecule of growth in situ on NiFe LDH-nanoarray for obtaining step (3) polymerize
Object MIP is immersed in eluant, eluent, and template molecule is carried out 20 min of elution at room temperature, is then taken out, no template point is obtained
Sub- molecularly imprinted polymer NIP；Continue to be embathed 4 times with deionized water, dries at room temperature, obtain ampicillin 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 ampicillin sensor of 7 embodiment 1 ~ 6 of embodiment preparation, applied to the detection of ampicillin, steps are as follows:
(1) standard solution is prepared: preparing the ampicillin standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: it is working electrode by ampicillin sensor, the various concentration prepared in inserting step (1)
Ampicillin standard solution 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 ampicillin standard solution containing various concentration is denoted asI i, the difference of response current strength reduction
Value is ΔI = I 0-I i, ΔIWith the mass concentration of ampicillin 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 ampicillin detection: replace the ampicillin standard solution in step (1) with sample to be tested, press
It is detected according to the method in step (2) and (3), the difference DELTA that current strength reduces according to responseIAnd working curve, obtain to
The content of ampicillin in sample.
The ampicillin sensor of 8 embodiment 1 ~ 6 of embodiment preparation is applied to ammonia according to the detecting step of embodiment 7
The detection in benzyl XiLin, the range of linearity are 0.0003 ~ 100 mmol/L, and detection is limited to 100 nmol/L.
The detection of ampicillin in 9 water sample of embodiment
Certain water sample is accurately pipetted, the ampicillin standard solution of certain mass concentration is added, the water of ampicillin not to be added
Sample is blank, carry out recovery testu, with embodiment 1 ~ 6 prepare ampicillin sensor, according to the step of embodiment 7 into
Row detection, measures the rate of recovery of ampicillin in water sample, and testing result is shown in Table 1:
The testing result of ampicillin in 1 water sample of table
1 testing result of table it is found that the relative standard deviation (RSD) of result less than 3.0 %, average recovery rate is 98.2 ~
100.4%, show that the present invention can be used for the detection of ampicillin in water sample, the high sensitivity of method, high specificity, as a result accurately
Reliably.
Claims (6)
1. a kind of preparation method of ampicillin sensor, which is characterized in that the ampicillin sensor is by the double gold of ferronickel
It is poly- without template molecule molecular engram to belong to growth in situ on layered hydroxide nano-chip arrays electrode NiFe LDH-nanoarray
Close what object NIP was obtained；The molecular engram polymerization that template molecule is free from without template molecule molecularly imprinted polymer NIP
Object；The molecularly imprinted polymer without containing template molecule is by the MIP of molecularly imprinted polymer containing template molecule by washing
Stripper plate molecule obtains；The MIP of molecularly imprinted polymer containing template molecule is that the molecular engram containing template molecule is poly-
Close object；The template molecule is ampicillin.
2. ferronickel bimetallic stratiform hydroxide nano chip arrays electrode NiFe LDH- as described in claim 1
Nanoarray, which is characterized in that the preparation method of the NiFe LDH-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, ferronickel bimetallic stratiform hydroxide nano chip arrays presoma electricity is prepared
Pole；
(4) the ferronickel bimetallic stratiform 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 ~ 40 DEG C at a temperature of reaction 4 ~ 6 hours after, take out
And embathed 2 ~ 4 times with deionized water, ferronickel bimetallic stratiform hydroxide nano chip arrays electrode NiFe LDH- is prepared
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 iron 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 NiFe LDH-nanoarray, and preparation method includes following system
Standby 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) NiFe LDH-nanoarray is clipped on Stirring device, the precursor mixed solution being inserted into step (2)
In, 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 drop/sec
Speed carries out initiation polymerization to 1 mmol azodiisobutyronitrile AIBN of mixed solution and dripping, on NiFe LDH-nanoarray
Obtain the MIP of molecularly imprinted polymer containing template molecule of growth in situ.
4. as described in claim 1 without template molecule molecularly imprinted polymer NIP, it is characterised in that the no template molecule
The preparation step of molecularly imprinted polymer NIP are as follows: will be given birth in situ on NiFe LDH-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 ampicillin sensor as described in claim 1 are as follows: will be obtained in NiFe in claim 2 ~ 4
The upper growth in situ of LDH-nanoarray without template molecule molecularly imprinted polymer NIP, embathe 2 ~ 4 times with deionized water, room temperature
Under dry, obtain ampicillin sensor.
6. using ampicillin sensor prepared by preparation method described in claim 1 ~ 5, the inspection applied to ampicillin
It surveys, which is characterized in that the detecting step is as follows:
(1) standard solution is prepared: preparing the ampicillin standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: it is working electrode by ampicillin sensor, the various concentration prepared in inserting step (1)
Ampicillin standard solution 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 ampicillin standard solution containing various concentration is denoted asI i, response electricity
The difference that intensity of flow reduces is ΔI = I 0-I i, ΔIWith the mass concentration of ampicillin standard solutionCBetween it is linear,
Draw ΔI?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 ampicillin detection: replace the ampicillin standard solution in step (1) with sample to be tested, press
It is detected according to the method in step (2) and (3), the difference DELTA that current strength reduces according to responseIAnd working curve, obtain to
The content of ampicillin in sample.
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