CN109342516A - A kind of preparation method and application of Sulfa drugs molecule electrochemical sensor - Google Patents
A kind of preparation method and application of Sulfa drugs molecule electrochemical sensor Download PDFInfo
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- CN109342516A CN109342516A CN201811306543.0A CN201811306543A CN109342516A CN 109342516 A CN109342516 A CN 109342516A CN 201811306543 A CN201811306543 A CN 201811306543A CN 109342516 A CN109342516 A CN 109342516A
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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 Sulfa drugs molecule electrochemical sensor.Belong to Nano-function thin films and biosensor technology field.The present invention is prepared for nickel 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 Sulfa drugs molecule as the molecularly imprinted polymer of template molecule on nickel 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 Sulfa drugs molecule electrochemical sensor just prepares 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
Sulfa drugs is a kind of general name of artificial synthesized antibacterials, is to align aminobenzene sulfonamide (abbreviation sulphur
Amine) be basic structure an analog derivative, because all so being referred to as sulfa drugs being containing P-aminobenzene-sulfonamide structure
More commonly used a kind of drug.Due to the hydrogen on sulfoamido, different types of sulfa drug can be formed by different heterocyclic substituteds.
They have many advantages, such as potency height, small toxicity, has a broad antifungal spectrum, oral easily absorption compared with parent sulfanilamide (SN).For example, sulfapryidine
Be it is the most frequently used, effect is most obvious, most representative sulfonamide, mainly to gram-positive bacteria and a part of Gram-negative
Bacterium has stronger inhibiting effect, is once widely used in the treatment of human intestine and respiratory disease.
Sulfa drugs antimicrobial spectrum is relatively wide, using simple, use cost is low, in many fields such as animal husbandry, aquaculture
It suffers from and is widely applied.However, due to the non-normal use of the mankind, every year about 20,000 ton of Sulfa drugs molecule into
Enter global environment.Sulfa drugs is abused or abused, serious joint stimulation, myalgia, Glenn Stevens Johnson can be caused
The allergic reactions such as syndrome, asthma seriously endanger human health.And sulfa drugs property is stable, distribution is wide in vivo, easily produces
Raw drug resistance, the metabolite in liver -- the solubility of acetylation sulfanilamide (SN) is low, and crystallization is precipitated easily in urine, causes the poison of kidney
Property, countries in the world are 100 μ g/kg to the maximum level of sulfa drugs in edible animal tissue.Currently, detection sulfonamides
The method of object molecule mainly has enzyme-linked immunization, high performance liquid chromatography, mass spectrography etc..Such method instrument is valuable, operation is multiple
Miscellaneous, laboratory personnel just can be carried out detection after needing professional training.Therefore, a kind of quick, highly selective and sensitive inspection is developed as early as possible
The method for surveying sulfa drugs 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 Sulfa drugs molecule electrochemical sensor, prepared electrochemical sensor, preparation is simple, favorable reproducibility,
Stability is strong, can be used for quick, the Sensitive Detection of Sulfa drugs molecule.Based on this purpose, the present invention disposably may be used first
It throws and is prepared for nickel hydroxide nano chip arrays on electrode, using its big specific surface area and high activity hydroxy functional group, and
The amido functional group of poly-dopamine is directly made on nickel hydroxide nano chip arrays in succession in succession using the method for growth in situ
For the poly-dopamine film containing electron mediator and using Sulfa drugs molecule as the molecularly imprinted polymer of template molecule,
After by template molecule elution, the position of template molecule originally has become hole, the i.e. molecular engram of eluted template molecule
Polymer, a kind of Sulfa drugs molecule electrochemical sensor just prepares completion as a result,.When for Sulfa drugs molecule into
When row detection, Sulfa drugs molecule electrochemical sensor is inserted into solution to be measured, the sulfa drugs in solution to be measured point
Son can be adsorbed onto the hole of NIP.Sulfa drugs molecule concentration in solution to be measured is bigger, is adsorbed onto sulphur in the hole of NIP
Amine drug molecule is more.When carrying out Electrochemical Detection, the intensity for detecting electric current can be with sulfanilamide (SN) in the hole for being adsorbed onto NIP
Class drug molecule increases and becomes smaller, being capable of sulphur in qualitative, quantitative solution to be measured thus according to the degree that current strength reduces
The concentration of amine drug molecule.
The technical solution adopted by the invention is as follows:
1. a kind of preparation method of Sulfa drugs molecule electrochemical sensor, the Sulfa drugs molecule electrochemistry is passed
Sensor is by growth in situ on nickel hydroxide nano chip arrays electrode Ni-nanoarray without template molecule molecularly imprinted polymer NIP
It obtains；The molecularly imprinted polymer that template molecule is free from without template molecule molecularly imprinted polymer NIP；It is described
The molecularly imprinted polymer without containing template molecule be by the MIP of molecularly imprinted polymer containing template molecule by eluted template point
What son obtained；The MIP of molecularly imprinted polymer containing template molecule is the molecularly imprinted polymer containing template molecule；It is described
Template molecule be Sulfa drugs molecule；
2. the preparation method of nickel hydroxide nano chip arrays electrode Ni-nanoarray described in technical solution 1 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 Nickelous nitrate hexahydrate Ni (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, nickel hydroxide nano chip arrays presoma electrode is prepared；
(4) the nickel hydroxide nano chip arrays presoma electrode insertion obtained step (3) contains dopamine, Ammonium Persulfate 98.5 and nitre
In the phosphate buffer solution PBS of sour cobalt, 20 ~ 40 DEG C at a temperature of reaction 4 ~ 6 hours after, take out simultaneously soaked with deionized water
It washes 2 ~ 4 times, nickel hydroxide nano chip arrays electrode Ni-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 system of the MIP of molecularly imprinted polymer containing template molecule of Ni-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) Ni-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 Ni-
The MIP of molecularly imprinted polymer containing template molecule of growth in situ is obtained on nanoarray；
4. the system without template molecule molecularly imprinted polymer NIP of Ni-nanoarray growth in situ described in technical solution 1
Standby step are as follows: by the molecular engram containing template molecule of growth in situ polymerize on Ni-nanoarray obtained in technical solution 3
Object MIP is immersed in eluant, eluent, and template molecule is carried out 5 ~ 20 min of elution at room temperature, is then taken out, no template is obtained
Molecular imprinted polymer NIP；The eluant, eluent is the mixed liquor of formic acid and methanol, wherein the volume ratio of formic acid and methanol
For 9:(1 ~ 5)；
5. the preparation step of Sulfa drugs molecule electrochemical sensor described in technical solution 1 are as follows: by technical solution 2 ~ 4
In the obtained growth in situ on Ni-nanoarray without template molecule molecularly imprinted polymer NIP, embathe 2 with deionized water
It ~ 4 times, dries at room temperature, obtains Sulfa drugs molecule electrochemical sensor；
6. being applied to using Sulfa drugs molecule electrochemical sensor prepared by technical solution described in technical solution 1 ~ 5
The detection of Sulfa drugs molecule, including following applying step:
(1) standard solution is prepared: the Sulfa drugs molecule standard for preparing one group of various concentration including blank standard specimen is molten
Liquid；
(2) working electrode is modified: being working electrode by Sulfa drugs molecule electrochemical sensor, is prepared in inserting step (1)
Various concentration Sulfa drugs molecule standard solution, hatch 10 min after take out, 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 Sulfa drugs molecule standard solution containing various concentration is denoted asI i,
The difference of response current strength reduction is ΔI = I 0-I i, ΔIWith the mass concentration of Sulfa drugs molecule standard solutionCBetween
It is linear, draw ΔI?CWorking curve；The phosphate buffer solution PBS concentration is 10 mmol/L, pH value is
7.4；Parameter setting when the described DPV detection are as follows: range and direction are 0 ~ 1 V, and stride is 0.05 V, burst length 0.05
S, sampling time are 0.016 s, and the pulse period is 0.5 s；
(4) in sample to be tested Sulfa drugs molecule detection: replace the Sulfa drugs molecule in step (1) with sample to be tested
Standard solution is detected according to the method in step (2) and (3), the difference DELTA that current strength reduces according to responseIAnd work
Curve obtains the content of Sulfa drugs molecule in sample to be tested；
7. Sulfa drugs molecule described in technical solution 1 ~ 6 is one of following Sulfa drugs molecule: sulfadimidine
SM2, bacteresulf SIZ, sulfametoxydiazine SMD, sulfadimethoxine SDM, phthalylsulfathiazol PST, sulphadiazine SD,
Sulfamethoxazole SMZ, sulfacetamide SA, silver sulfadiazine SD-Ag, sulfamylon SML.
Beneficial achievement of the invention
(1) Sulfa drugs molecule electrochemical sensor preparation of the present invention is simple, easy to operate, realizes to sample
Quickly, sensitive, highly selective detection, and it is at low cost, it can be applied to portable inspectiont, there is market development prospect；
(2) growth in situ molecular engram polymerize the present invention on nickel hydroxide nano chip arrays electrode Ni-nanoarray for the first time
On the one hand object can grow more, molecularly imprinted polymer more evenly using the big specific surface area of Ni-nanoarray, and
Ni-nanoarray has excellent electron transmission ability, to greatly improve detection sensitivity；On the other hand, the present invention will be more
When on bar amine in-situ polymerization to nickel hydroxide 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 is rich in using nickel hydroxide nano chip arrays high activity hydroxy functional group and big specific surface area with
Dopamine combines, sufficiently thin poly- more being formed so that dopamine is in nickel hydroxide nano chip arrays in situ Polymerization
While bar amine film, on uniform fold to nickel hydroxide nano chip arrays, thus for more better polymerizable moleculars in next step
Imprinted polymer carries out place mat；Later using poly-dopamine to the amino being rich on hydroxy functional group and molecularly imprinted polymer
Strong connection function, then dexterously use Ni-nanoarray as blender, in molecular engram precursor mixed solution
Immersion stirring is carried out, by control mixing speed, the rate of addition and polymeric reaction temperature of initiators for polymerization, in Ni-
The surface nanoarray direct in-situ grows the molecularly imprinted polymer that can control film thickness, on the one hand makes Ni-
Nanoarray can secured supporting molecular imprinted polymer, to significantly improve the stability of prepared electrochemical sensor
And reproducibility；On the other hand molecularly imprinted polymer can effectively be controlled in the film forming thickness of electrode surface, solving can not control
Molecular engram film processed is unable to control the technical problem so as to cause poor reproducibility in electrode surface film forming thickness；In addition, more due to
Preparation method of the invention can sufficiently improve molecule print to the in-stiu coating of the effective control and electron mediator of film forming thickness
The sensitivity of electrochemical sensor based on mark and detection limit have important scientific meaning and application value.
Specific embodiment
The preparation of 1 Ni-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 Nickelous nitrate hexahydrate Ni (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, nickel hydroxide nano chip arrays presoma electrode is prepared；
(4) the nickel hydroxide nano chip arrays presoma electrode insertion obtained step (3) contains dopamine, Ammonium Persulfate 98.5 and nitre
In the phosphate buffer solution PBS of sour cobalt, 20 DEG C at a temperature of reaction 4 hours after, take out simultaneously embathed 2 times with deionized water,
Nickel hydroxide nano chip arrays electrode Ni-nanoarray is prepared；
The electrode therein that can disposably throw is nickel foam；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 Ni-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 Nickelous nitrate hexahydrate Ni (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, nickel hydroxide nano chip arrays presoma electrode is prepared；
(4) the nickel hydroxide nano chip arrays presoma electrode insertion obtained step (3) contains dopamine, Ammonium Persulfate 98.5 and nitre
In the phosphate buffer solution PBS of sour cobalt, 30 DEG C at a temperature of reaction 5 hours after, take out simultaneously embathed 3 times with deionized water,
Nickel hydroxide nano chip arrays electrode Ni-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 Ni-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 Nickelous nitrate hexahydrate Ni (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, nickel hydroxide nano chip arrays presoma electrode is prepared；
(4) the nickel hydroxide nano chip arrays presoma electrode insertion obtained step (3) contains dopamine, Ammonium Persulfate 98.5 and nitre
In the phosphate buffer solution PBS of sour cobalt, 40 DEG C at a temperature of reaction 6 hours after, take out simultaneously embathed 4 times with deionized water,
Nickel hydroxide nano chip arrays electrode Ni-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.
The preparation method of 4 Sulfa drugs molecule electrochemical 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) Ni-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 carry out initiation polymerization to 1 mmol azodiisobutyronitrile AIBN of mixed solution and dripping, obtained on Ni-nanoarray
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 Ni-nanoarray for obtaining step (3) soaks
Not in eluant, eluent, template molecule is subjected to 5 min of elution at room temperature, is then taken out, obtains no template molecule molecule print
Mark polymer NIP；Continue to be embathed 2 times with deionized water, dries at room temperature, obtain Sulfa drugs molecule electrochemical sensing
Device；
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 Sulfa drugs molecule electrochemical 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) Ni-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 carry out initiation polymerization to 1 mmol azodiisobutyronitrile AIBN of mixed solution and dripping, obtained on Ni-nanoarray
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 Ni-nanoarray for obtaining step (3) soaks
Not in eluant, eluent, template molecule is subjected to 10 min of elution at room temperature, is then taken out, obtains no template molecule molecule print
Mark polymer NIP；Continue to be embathed 3 times with deionized water, dries at room temperature, obtain Sulfa drugs molecule electrochemical sensing
Device；
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 Sulfa drugs molecule electrochemical 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) Ni-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 carry out initiation polymerization to 1 mmol azodiisobutyronitrile AIBN of mixed solution and dripping, obtained on Ni-nanoarray
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 Ni-nanoarray for obtaining step (3) soaks
Not in eluant, eluent, template molecule is subjected to 20 min of elution at room temperature, is then taken out, obtains no template molecule molecule print
Mark polymer NIP；Continue to be embathed 4 times with deionized water, dries at room temperature, obtain Sulfa drugs molecule electrochemical sensing
Device；
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 Sulfa drugs molecule sensor of 7 embodiment 1 ~ 6 of embodiment preparation, the inspection applied to Sulfa drugs molecule
It surveys, steps are as follows:
(1) standard solution is prepared: the Sulfa drugs molecule standard for preparing one group of various concentration including blank standard specimen is molten
Liquid；
(2) working electrode is modified: being working electrode by Sulfa drugs molecule electrochemical sensor, is prepared in inserting step (1)
Various concentration Sulfa drugs molecule standard solution, hatch 10 min after take out, 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 Sulfa drugs molecule standard solution containing various concentration is denoted asI i, response current intensity drop
Low difference is ΔI = I 0-I i, ΔIWith the mass concentration of Sulfa drugs molecule standard solutionCBetween it is linear, draw
Δ processedI?CWorking curve；The PBS is the phosphate buffer solution of 10 mmol/L, the phosphate buffer solution
PH value is 7.4；Parameter setting when the described DPV detection are as follows: range and direction are 0 ~ 1 V, and stride is 0.05 V, burst length
For 0.05 s, the sampling time is 0.016 s, and the pulse period is 0.5 s；
(4) in sample to be tested Sulfa drugs molecule detection: replace the Sulfa drugs molecule in step (1) with sample to be tested
Standard solution is detected according to the method in step (2) and (3), the difference DELTA that current strength reduces according to responseIAnd work
Curve obtains the content of Sulfa drugs molecule in sample to be tested.
The Sulfa drugs molecule sensor of 8 embodiment 1 ~ 6 of embodiment preparation, is answered according to the detecting step of embodiment 7
For the detection of different Sulfa drugs molecules, the range of linearity and detection limit are shown in Table 1:
The detection technique index of 1 Sulfa drugs molecule of table
The detection of Sulfa drugs molecule in 9 pig urine samples of embodiment
Pig urine samples are accurately pipetted, the Sulfa drugs molecule standard solution of certain mass concentration are added, sulfamido not to be added
The pig urine samples of drug molecule are blank, carry out recovery testu, the Sulfa drugs molecule sensing prepared with embodiment 1 ~ 6
Device is detected according to the step of embodiment 7, measures the rate of recovery of Sulfa drugs molecule in pig urine samples, and testing result is shown in
Table 2:
The testing result of Sulfa drugs molecule in 2 pig urine samples of table
For 2 testing result of table it is found that the relative standard deviation (RSD) of result is less than 3.0 %, average recovery rate is 98.0 ~ 101%,
Show that the present invention can be used for the detection of a variety of Sulfa drugs molecules in pig urine, the high sensitivity of method, high specificity are as a result quasi-
It is really reliable.
The detection of Sulfa drugs molecule in 10 water sample of embodiment
Certain water sample is accurately pipetted, the Sulfa drugs molecule standard solution of certain mass concentration is added, sulfamido not to be added
The water sample of drug molecule be blank, carry out recovery testu, with embodiment 1 ~ 6 prepare Sulfa drugs molecule sensor,
It is detected according to the step of embodiment 7, measures the rate of recovery of Sulfa drugs molecule in water sample, testing result is shown in Table 3:
The testing result of Sulfa drugs molecule in 3 water sample of table
3 testing result of table it is found that the relative standard deviation (RSD) of result less than 2.5 %, average recovery rate is 99.0 ~
100.4%, show that the present invention can be used for the detection of a variety of Sulfa drugs molecules in water sample, high sensitivity, the specificity of method
By force, as a result accurately and reliably.
Claims (7)
1. a kind of preparation method of Sulfa drugs molecule electrochemical sensor, which is characterized in that the sulfa drugs point
Sub- electrochemical sensor is printed by growth in situ on nickel hydroxide nano chip arrays electrode Ni-nanoarray without template molecule molecule
Mark polymer NIP is obtained；The molecular engram that template molecule is free from without template molecule molecularly imprinted polymer NIP
Polymer；The molecularly imprinted polymer without containing template molecule is passed through by the MIP of molecularly imprinted polymer containing template molecule
Cross what eluted template molecule obtained；The MIP of molecularly imprinted polymer containing template molecule is the molecule print containing template molecule
Mark polymer；The template molecule is Sulfa drugs molecule.
2. nickel hydroxide nano chip arrays electrode Ni-nanoarray as described in claim 1 is it is characterized in that, the Ni-
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 Nickelous nitrate hexahydrate Ni (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, nickel hydroxide nano chip arrays presoma electrode is prepared；
(4) the nickel hydroxide nano chip arrays presoma electrode insertion obtained step (3) contains dopamine, Ammonium Persulfate 98.5 and nitre
In the phosphate buffer solution PBS of sour cobalt, 20 ~ 40 DEG C at a temperature of reaction 4 ~ 6 hours after, take out simultaneously soaked with deionized water
It washes 2 ~ 4 times, nickel hydroxide nano chip arrays electrode Ni-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 Ni-nanoarray, and 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) Ni-nanoarray is clipped on Stirring device, is inserted into the precursor mixed solution in step (2), in N2Ring
At a temperature of border 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 mixed
1 mmol azodiisobutyronitrile AIBN is added dropwise in conjunction solution and carries out initiation polymerization, growth in situ is obtained on Ni-nanoarray
The 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 molecule
The preparation step of molecularly imprinted polymer NIP are as follows: by growth in situ contains on Ni-nanoarray obtained in claim 3
Template molecule molecularly imprinted polymer MIP is immersed in eluant, eluent, template molecule is carried out 5 ~ 20 min of elution at room temperature, so
After take out, obtain no template molecule molecularly imprinted polymer NIP；The eluant, eluent is the mixed liquor of formic acid and methanol,
The volume ratio of middle formic acid and methanol is 9:(1 ~ 5).
5. the preparation step of Sulfa drugs molecule electrochemical sensor as described in claim 1 are as follows: will be in claim 2 ~ 4
The growth in situ obtained on Ni-nanoarray without template molecule molecularly imprinted polymer NIP, embathe 2 ~ 4 with deionized water
It is secondary, it dries at room temperature, obtains Sulfa drugs molecule electrochemical sensor.
6. being applied to using Sulfa drugs molecule electrochemical sensor prepared by preparation method described in claim 1 ~ 5
The detection of Sulfa drugs molecule, which is characterized in that the detecting step is as follows:
(1) standard solution is prepared: the Sulfa drugs molecule standard for preparing one group of various concentration including blank standard specimen is molten
Liquid；
(2) working electrode is modified: being working electrode by Sulfa drugs molecule electrochemical sensor, is prepared in inserting step (1)
Various concentration Sulfa drugs molecule standard solution, hatch 10 min after take out, 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 Sulfa drugs molecule standard solution containing various concentration is denoted asI i,
The difference of response current strength reduction is ΔI = I 0-I i, ΔIWith the mass concentration of Sulfa drugs molecule standard solutionCBetween
It is linear, draw ΔI?CWorking curve；The phosphate buffer solution PBS concentration is 10 mmol/L, and pH value is
7.4；Parameter setting when the described DPV detection are as follows: range and direction are 0 ~ 1 V, and stride is 0.05 V, burst length 0.05
S, sampling time are 0.016 s, and the pulse period is 0.5 s；
(4) in sample to be tested Sulfa drugs molecule detection: replace the Sulfa drugs molecule in step (1) with sample to be tested
Standard solution is detected according to the method in step (2) and (3), the difference DELTA that current strength reduces according to responseIAnd work
Curve obtains the content of Sulfa drugs molecule in sample to be tested.
7. the Sulfa drugs molecule as described in claim 1 ~ 6 is one of following Sulfa drugs molecule: sulfadimidine
SM2, bacteresulf SIZ, sulfametoxydiazine SMD, sulfadimethoxine SDM, phthalylsulfathiazol PST, sulphadiazine SD,
Sulfamethoxazole SMZ, sulfacetamide SA, silver sulfadiazine SD-Ag, sulfamylon SML.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110501402A (en) * | 2019-09-24 | 2019-11-26 | 山东农业大学 | A kind of electrochemical sensor and its detection method of super sensitivity detection sulphathiazole |
| CN111307916A (en) * | 2020-03-02 | 2020-06-19 | 宁波职业技术学院 | Preparation method of bimetallic nickel cobaltate molecular imprinting array sensor and application of bimetallic nickel cobaltate molecular imprinting array sensor in detection of residual sulfonamides |
| CN111551602A (en) * | 2020-07-02 | 2020-08-18 | 盐城工学院 | Preparation method of sulfadimethoxine molecular imprinting electrochemical sensor |
| CN113042075A (en) * | 2019-12-27 | 2021-06-29 | 四川大学 | Method for preparing cobalt phosphide/carbon composite material by using baker's yeast through impregnation method |
| CN113252754A (en) * | 2021-05-19 | 2021-08-13 | 郑州大学 | Electrochemical immunosensor for detecting sulfadimethoxine and preparation method thereof |
| CN113533475A (en) * | 2021-07-12 | 2021-10-22 | 武汉海关技术中心 | Multi-component sulfonamide antibiotic paper-based microfluidic analysis device and analysis method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103926286A (en) * | 2014-04-25 | 2014-07-16 | 广西民族大学 | High-sensitivity nanometer cobalt oxide-doped talampicillin molecular imprinting electrochemical sensor and preparation method thereof |
| CN104191702A (en) * | 2014-06-16 | 2014-12-10 | 华中科技大学 | Nanometer cobalt hydroxide-graphene composite membrane and preparation method and application thereof |
| CN104558409A (en) * | 2013-10-22 | 2015-04-29 | 北京林业大学 | Surface molecular imprinting polymer made from nanoflower material, and preparation and application of surface molecular imprinting polymer |
| CN105891290A (en) * | 2016-04-01 | 2016-08-24 | 肇庆学院 | Magnetic molecular imprinting electrochemical sensor used for detecting trace sulfadimidine |
-
2018
- 2018-11-05 CN CN201811306543.0A patent/CN109342516B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558409A (en) * | 2013-10-22 | 2015-04-29 | 北京林业大学 | Surface molecular imprinting polymer made from nanoflower material, and preparation and application of surface molecular imprinting polymer |
| CN103926286A (en) * | 2014-04-25 | 2014-07-16 | 广西民族大学 | High-sensitivity nanometer cobalt oxide-doped talampicillin molecular imprinting electrochemical sensor and preparation method thereof |
| CN104191702A (en) * | 2014-06-16 | 2014-12-10 | 华中科技大学 | Nanometer cobalt hydroxide-graphene composite membrane and preparation method and application thereof |
| CN105891290A (en) * | 2016-04-01 | 2016-08-24 | 肇庆学院 | Magnetic molecular imprinting electrochemical sensor used for detecting trace sulfadimidine |
Non-Patent Citations (2)
| Title |
|---|
| AMIR HATAMIE等: "Green synthesis of graphitic carbon nitride nanosheet (g-C3N4) and using it as a label-free fluorosensor for detection of metronidazole via quenching of the fluorescence", 《TALANTA》 * |
| XUE LI等: "A Sensitive and Renewable Chlortoluron Molecularly Imprinted Polymer Sensor Based on the Gate-Controlled Catalytic Electrooxidation of H2O2 on Magnetic Nano-NiO", 《ELECTROANALYSIS》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110501402A (en) * | 2019-09-24 | 2019-11-26 | 山东农业大学 | A kind of electrochemical sensor and its detection method of super sensitivity detection sulphathiazole |
| CN113042075A (en) * | 2019-12-27 | 2021-06-29 | 四川大学 | Method for preparing cobalt phosphide/carbon composite material by using baker's yeast through impregnation method |
| CN111307916A (en) * | 2020-03-02 | 2020-06-19 | 宁波职业技术学院 | Preparation method of bimetallic nickel cobaltate molecular imprinting array sensor and application of bimetallic nickel cobaltate molecular imprinting array sensor in detection of residual sulfonamides |
| CN111551602A (en) * | 2020-07-02 | 2020-08-18 | 盐城工学院 | Preparation method of sulfadimethoxine molecular imprinting electrochemical sensor |
| CN113252754A (en) * | 2021-05-19 | 2021-08-13 | 郑州大学 | Electrochemical immunosensor for detecting sulfadimethoxine and preparation method thereof |
| CN113533475A (en) * | 2021-07-12 | 2021-10-22 | 武汉海关技术中心 | Multi-component sulfonamide antibiotic paper-based microfluidic analysis device and analysis method |
| CN113533475B (en) * | 2021-07-12 | 2023-11-14 | 武汉海关技术中心 | Multi-component sulfonamide antibiotic paper-based microfluidic analysis device and analysis method |
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