CN109001280A - A kind of preparation of thiabendazole molecular imprinting electrochemical sensor and application method - Google Patents
A kind of preparation of thiabendazole molecular imprinting electrochemical sensor and application method Download PDFInfo
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- CN109001280A CN109001280A CN201810945250.0A CN201810945250A CN109001280A CN 109001280 A CN109001280 A CN 109001280A CN 201810945250 A CN201810945250 A CN 201810945250A CN 109001280 A CN109001280 A CN 109001280A
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Abstract
The invention discloses a kind of preparation of thiabendazole molecular imprinting electrochemical sensor and application methods, the following steps are included: modification graphene oxide obtains graphene oxide modified electrode on polishing electrode first, then graphene oxide modified electrode is subjected to electroreduction in sodium chloride solution and obtains redox graphene modified electrode.Then, in redox graphene modified electrode surface in situ electropolymerization molecularly imprinted polymer, one layer of molecular engram film is formed.For molecular engram film using o-phenylenediamine and Resorcino as function monomer, thiabendazole is template molecule.After removing thiabendazole template molecule, the thiabendazole molecular imprinting electrochemical sensor based on redox graphene is obtained.The sensor is combined with differential pulse voltammetry, trace thiabendazole can be detected.High sensitivity, selectivity are good, have application value in Safety of Food Quality detection and environmental monitoring field.
Description
Technical field
The invention belongs to sample pre-treatments and electrochemical polymerization technical field, and in particular to a kind of thiabendazole molecular engram
The preparation of electrochemical sensor and application method.
Background technique
Thiabendazole (Thiabendazole, TBZ) is broad spectrum activity antifungal agent, and with absorbability, i.e., it can pass through transpiration
It flows and operates distribution in entire plant, there is very long residual effect.Its controllable infection, and can inhibit gemma germination, interference
Mycelial growth, and influence conidial formation；It can also be used for fruit freshness preserving, concrete application can be made into colloidal suspending agent, liquor
Deng for soaking fruit；It can also be used for the fruit storages phase such as citrus, banana anti-corrosion.After antistaling agent is used for fruit and vegetable picking, due to interior suction
Property, permeable pericarp enters pulp, causes the residual can't be washed off clearly, to human liver, kidney, nervous system with certain toxicity.
In order to ensure the safety of consumer, various countries have formulated corresponding rule and standard, it is specified that antistaling agent in food
Maximum residue limit.European Union, Japan, the U.S. provide that the dosage of TBZ in citrus fruit must not exceed 6,10,10mgkg-1, China
Limited amount is 10mgkg-1.Maximum permission quantity: fruit 3.0mg/kg, vegetables 2.0mg/kg, beet 0.1mg/kg, ox, sheep,
It is 0.1mg/kg, milk 0.05mg/kg, potato 0.02mg/kg in pork.Therefore, residue detection ten is carried out to thiabendazole
Point it is necessary to.Common thiabendazole detection means specifically includes that gas chromatography-mass spectrography, high performance liquid chromatography, efficient liquid phase
Chromatography mass spectrometry.These methods and results detectabilities are strong, accuracy is high, but need large-scale instrument and equipment, and discomfort is examined on site
It surveys.
Compared to traditional detecting instrument, electrochemical sensor have instrument be simple and convenient to operate, high sensitivity, cost
Low advantage is widely used in the fields such as environmental monitoring and Safety of Food Quality detection.But Electrochemical Detection disturbing factor is more, choosing
Selecting property is not high.
Molecularly imprinted polymer has good identification selection to template molecule.Using molecularly imprinted polymer as sensing
The molecular imprinting electrochemical sensor of device sensitive material, a ready-made important directions for molecular imprinting technology application study.Point
Target may be implemented since its preparation is simple, detection limit is low, does not need complicated sample pre-treatments in sub- trace electrochemical sensor
The on-line monitoring of object causes the extensive interest of people, becomes the hot spot studied both at home and abroad.
Molecular engram sensor is usually that molecularly imprinted polymer (film) is as recognition component and solid by appropriate ways
It is scheduled on transducer face, when testing molecule is in conjunction with recognition component, generates physics or chemical signal, converter turns this signal
It changes the output signal (electric current, capacitor etc.) that can be quantified into, the spy to testing molecule is realized by monitoring output signal
Opposite sex identification.During Electrochemical Detection, the imprinted sites in object and polymeric membrane are specifically bound, and lead to electrochemistry
The oxidation peak current of probe changes, and within the scope of a certain concentration, concentration and electrochemical probe the oxidation peak electricity of object
The knots modification of stream is in a linear relationship, to realize the quantitative detection of object.
Graphene oxide (GO) is although have good processability, since the introducing of a large amount of oxygen-containing functional groups is broken
It is broken the conjugation region of graphene, its electric conductivity is reduced, limits its scope of application.GO can partially repair it by reduction
Certain electric conductivity is restored in conjugation region, while remaining oxygen-containing functional group can also urge for adsorbing and fixing for object with electricity
Change and active site is provided.Therefore, redox graphene (rGO) has been widely used in electrochemical sensor, for raising pair
The absorption property and detection sensitivity of target molecule.
Electrochemical polymerization method is that electrochemical polymerization, structure occurs with function monomer molecule in the presence of microsphere
At it is a kind of include microsphere polymeric membrane.Electrochemical polymerization is easy to operate, containing function monomer and microsphere
Electropolymerization is carried out in solution can be realized.Repeated excellent surpass can be obtained on conductive matrices by the amount of control circulation charge
Film can reach nanometer grade thickness, this is that conventional method is not achieved, especially suitable in thicker polymer film
Spread hindered effect and the biggish microsphere of molecular dimension.
Electropolymerization frequently with method have potentiostatic method, galvanostatic method and cyclic voltammetry.Wherein cyclic voltammetry can
The formation that thin polymer film is observed according to continuous cyclic voltammogram is conducive to understand entire polymerization process, can be with
The method of circle number is scanned successfully to prepare the thin polymer film of consistency of thickness using fixed cycles, and the reproducibility of electrode is fabulous.
Currently, having no the report of thiabendazole molecular imprinting electrochemical sensor.
Summary of the invention
The main object of the present invention is to realize the on-line monitoring of thiabendazole, overcomes the limitation of traditional detection method, and
Prepare a kind of thiabendazole molecular imprinting electrochemical sensor.
To achieve the above object, the following technical scheme is adopted:
1, a kind of preparation method of thiabendazole molecular imprinting electrochemical sensor, comprising the following steps:
(1), glass-carbon electrode is handled: for glass-carbon electrode (GCE, diameter 3mm) before use, with polishing pad, successively using partial size is 1
μm, 0.3 μm, 0.03 μm of α-Al2O3Powder polishes (8-shaped or zigzag) polishing 2min.Electrode after polishing every time, is successively used
Hydrochloric acid (V/V, 1: 1), dehydrated alcohol, deionized water be cleaned by ultrasonic 3min.Electrode is placed in 5.0mmol LK3[Fe(CN)6]/K4
[Fe(CN)6]+0.1mol/L KCl solution in carry out cyclic voltammetry scan, scanning potential range is -0.2~+0.6V, scanning
Rate is 50mV/s, until stable voltammogram is obtained, it is spare after electrode taking-up is dried.
(2), graphene oxide modified electrode: weighing 50mg graphene oxide with assay balance, be dissolved in 50mL go from
In sub- water (ultrasonic dissolution 30min), it is prepared into 1.0mgmL-1Graphene oxide solution.Draw 10 μ L's with micro-sampling pin
GO solution, the glassy carbon electrode surface being added dropwise in polishing obtain graphene oxide modified electrode using infrared light irradiation 10min.
(3), it electroreduction graphene oxide: takes 40mL NaCl (0.5M) in 50mL electrolytic cell with graduated cylinder, electrolytic cell is set
In stirring on magnetic stirring apparatus, and nitrogen 10min is passed through into solution, whole experiment process all carries out under nitrogen atmosphere.It will
Electrode after GO modification immerses in above-mentioned suspension, carries out electrochemical reduction to GO with cyclic voltammetry, experiment condition: scanning electricity
Pressure: -1.7V~0.2V, scanning circle number: 8 circles, sweep speed: 50mVs-1, obtain redox graphene modified electrode.
(4), the preparation of thiabendazole molecular engram film: the amount of the substances such as o-phenylenediamine and Resorcino is mixed, and is added
The phosphate buffer solution of 30mL quickly stirs ultrasonic deoxygenation 10min simultaneously.The thiabendazole of 0.0205g is added to 20mL
Methanol solution in, ultrasonic dissolution 1min mixes obtained solution with above-mentioned solution, then into solution lead to nitrogen 3min, into
One step removes the oxygen (at electric polymerization reaction initial stage, oxygen meeting attack anode free radical) in solution, then reduces nitrogen flow,
Continuation is tested under nitrogen atmosphere.ERGO modified electrode is put into electrolytic cell, prepares thiophene benzene miaow using cyclic voltammetry
Azoles molecular imprinting electrochemical sensor, condition setting: sweep speed 40mV/s, scanning voltage: -0.2~0.8V, scanning circle number:
10 circles, can obtain imprinted polymer film in glassy carbon electrode surface.The preparation of non-blotting membrane removes as trace membrane preparation method
It is not added outside template molecule.
The redox graphene modified electrode for being coated with thiabendazole molecular engram film is immersed in the hydrochloric acid solution of 0.5M,
It stirs at low speed elution 10min and removes thiabendazole therein, electrode is rinsed after taking out with deionized water, spare with being dried with nitrogen.
Molecular engram film preparation process uses three-electrode system: with glass-carbon electrode (Φ=3mm) for working electrode, silver-chlorine
Change silver electrode is reference electrode, platinum electrode is to electrode.Since thiabendazole has preferable dissolubility in an acidic solution, and
Hydrochloric acid solution can destroy the hydrogen bond formed between thiabendazole and function monomer, and the hydrochloric acid of low concentration there will not be polymeric membrane
Biggish destructiveness obtains thiabendazole molecular imprinting electrochemical so as to elute thiabendazole from polymer
Sensor realizes the specific detection of thiabendazole.
2, the application method of thiabendazole molecular imprinting electrochemical sensor, comprising the following steps:
(1) sample solution of suitable volumes, centrifuge separation are measured.The filter membrane that centrifugate crosses 0.45 μm is filtered again,
Collect supernatant.
(2) thiabendazole content is measured using one differential pulse method of thiabendazole molecular imprinting electrochemical sensor.
Compared with prior art, the invention has the benefit that
(1) compared with traditional detection method, electrochemical sensor detection do not need complicated pre-treatment, it is easy to operate,
The time-consuming short, scene of can carrying out and on-line checking.
(2) the thiabendazole molecular imprinting electrochemical sensor based on redox graphene electrode, increases electrode
Specific surface area contributes to form more recognition sites, and the current-responsive of electrode can be improved and improve the detection of thiabendazole
Limit.
(3) using o-phenylenediamine and Resorcino as bi-functional monomer, the polymer film knot of electropolymerization preparation can be overcome
Structure is single, rigidly has a surplus and flexible insufficient problem, is easy to synthesize thiophene benzene in glassy carbon electrode surface voltolisation using cyclic voltammetry
Imidazole molecule blotting membrane.
Specific embodiment
The present invention is described in further details below by example, these examples are only used to illustrate the present invention, and unlimited
The scope of the present invention processed.
Embodiment 1
The preparation method of thiabendazole molecular imprinting electrochemical sensor, comprising the following steps:
(1), glass-carbon electrode is handled: for glass-carbon electrode (GCE, diameter 3mm) before use, with polishing pad, successively using partial size is 1
μm, 0.3 μm, 0.03 μm of α-Al2O3Powder polishes (8-shaped or zigzag) polishing 2min.Electrode after polishing every time, is successively used
Hydrochloric acid (V/V, 1: 1), dehydrated alcohol, deionized water be cleaned by ultrasonic 3min.Electrode is placed in 5.0mmol LK3[Fe(CN)6]/K4
[Fe(CN)6]+0.1mol/L KCl solution in carry out cyclic voltammetry scan, scanning potential range is -0.2~+0.6V, scanning
Rate is 50mV/s, until stable voltammogram is obtained, it is spare after electrode taking-up is dried.
(2), graphene oxide modified electrode: weighing 50mg graphene oxide with assay balance, be dissolved in 50mL go from
In sub- water (ultrasonic dissolution 30min), it is prepared into 1.0mgmL-1Graphene oxide solution.Draw 10 μ L's with micro-sampling pin
GO solution, the glassy carbon electrode surface being added dropwise in polishing obtain graphene oxide modified electrode using infrared light irradiation 10min.
(3), it electroreduction graphene oxide: takes 40mL NaCl (0.5M) in 50mL electrolytic cell with graduated cylinder, electrolytic cell is set
In stirring on magnetic stirring apparatus, and nitrogen 10min is passed through into solution, whole experiment process all carries out under nitrogen atmosphere.It will
Electrode after GO modification immerses in above-mentioned suspension, carries out electrochemical reduction to GO with cyclic voltammetry, experiment condition: scanning electricity
Pressure: -1.7V~0.2V, scanning circle number: 8 circles, sweep speed: 50mVs-1, obtain redox graphene modified electrode.
(4), the preparation of thiabendazole molecular engram film: the amount of the substances such as o-phenylenediamine and Resorcino is mixed, and is added
The phosphate buffer solution of 30mL quickly stirs ultrasonic deoxygenation 10min simultaneously.The thiabendazole of 0.0205g is added to 20mL
Methanol solution in, ultrasonic dissolution 1min mixes obtained solution with above-mentioned solution, then into solution lead to nitrogen 3min, into
One step removes the oxygen (at electric polymerization reaction initial stage, oxygen meeting attack anode free radical) in solution, then reduces nitrogen flow,
Continuation is tested under nitrogen atmosphere.ERGO modified electrode is put into electrolytic cell, prepares thiophene benzene miaow using cyclic voltammetry
Azoles molecular imprinting electrochemical sensor, condition setting: sweep speed 40mV/s, scanning voltage: -0.2~0.8V, scanning circle number:
10 circles, can obtain imprinted polymer film in glassy carbon electrode surface.The preparation of non-blotting membrane removes as trace membrane preparation method
It is not added outside template molecule.
The redox graphene modified electrode for being coated with thiabendazole molecular engram film is immersed in the hydrochloric acid solution of 0.5M,
It stirs at low speed elution 10min and removes thiabendazole therein, electrode is rinsed after taking out with deionized water, spare with being dried with nitrogen.
Molecular engram film preparation process uses three-electrode system: with glass-carbon electrode (Φ=3mm) for working electrode, silver-silver chloride electrode
It is to electrode for reference electrode, platinum electrode.
Embodiment 2
The preparation condition of thiabendazole molecular imprinting electrochemical sensor is optimized, comprising the following steps:
1), the optimization of electropolymerization liquid type: the HAC-NaAC, NaH of 0.1M are selected respectively2PO4-Na2HPO4, NH3-NH4Cl
Supporting electrolyte is done, the mixed solution of monomer can form polymer film in electrode surface, when according to the elution of template molecule
Between length, the insulating properties of film, the peak current size completely after elution and heavily adsorb performance select suitable polymer fluid.Wherein exist
NaH2PO4-Na2HPO4The film good insulating prepared in solution, stability, current responsing signal are best.
2), the optimization of electropolymerization liquid pH: pH value has a certain impact to the formation of o-phenylenediamine and Resorcino polymeric membrane.
It is that 5,6,7,8,9,10, the 11 PBS electropolymerization liquid of 0.1M is tested that pH is selected in experiment, by resulting electropolymerization film, according to
Trace electrode completely after elution determines polymer fluid most the current-responsive value size before and after standard liquid absorption in detection solution
Excellent pH.Wherein, best in the electrode insulation of the pH phosphate solution electropolymerization preparation for being 9, and completely after elution, difference arteries and veins
Voltammetry (DPV) peak current maximum is rushed, current-responsive value is maximum.
3), the optimization of electropolymerization circle number: electrochemical polymerization film forming can scan circle number by control, prepare suitable depth
Film.When one timing of sweep speed, polymerization circle number is very few, and electrode surface can not be completely covered than relatively thin in electropolymerization film obtained,
And it is also easy to fall off from electrode surface during elution；If polymerization circle number it is excessive, will lead to template molecule embedding it is too deep,
It is difficult to be eluted with eluting solvent, the imprinted cavity of formation is very few.Experiment selects the phosphoric acid buffer that pH is 9,0.1M molten
Liquid prepares thiabendazole molecular engram film with the sweep speed of 40mV/s, 10 circle of electropolymerization.
4), the selection of eluting solvent: after the completion of electropolymerization, by modified electrode in dilute hydrochloric acid (0.5M), methanol-hydrogen sodium oxide molybdena
(V/V, 3: 1), methanol-acetic acid (V/V, 3: 1), in four kinds of solution of methanol eluted, every 3min, detection elution effect.It is real
Test and show: methanol-hydrogen sodium oxide molybdena (V/V, 3: 1), methanol-acetic acid (V/V, 3: 1) in mixed liquor, non-blotting membrane being eluted
When, it may appear that biggish CV redox peaks show that both eluting solvents can destroy polymeric membrane；It is eluted in methanol solution
When, not only elution time is long, but also elution is not thorough, obtained CV oxidation peak current value very little；It is stirred in the dilute hydrochloric acid of 0.5M
When mixing elution, blotting membrane does not fall off and destroys, and significant change does not occur for non-blotting membrane, shows: trace polymerization film is in 0.5M
Hydrochloric acid solution in be stabilized.
Embodiment 3
The present invention has investigated embodiment using differential pulse voltammetry and has prepared thiabendazole molecular imprinting electrochemical sensor
Response to the thiabendazole of various concentration.Electrode is immersed in the methanol solution containing a certain concentration thiabendazole, enrichment
9min rinses electrode surface with deionized water, then electrode is placed in detection liquid and carries out DPV scanning, the concentration range of thiabendazole
For 0.1-24 μ g/mL, current potential: -0.2~+0.6V is scanned.In detection range, the current responsing signal of electrode is with thiophene benzene miaow
The increase of azoles concentration and gradually decrease, show the increase with thiabendazole concentration, blotting membrane to the adsorbance of thiabendazole by
Cumulative big, marking recognition site (hole) is reduced, and the potassium ferricyanide/potassium ferrocyanide is caused to be difficult to reach electrode table across blotting membrane
Face participates in electrochemical reaction.Finally, equilibrium state is reached to the absorption of thiabendazole with blotting membrane, response current tends to be steady
It is fixed.In the concentration range of 0.1-2 μ g/mL and 2-24 μ g/mL, the concentration C and response peak current Δ I of thiabendazole are formed well
Linear relationship, sensor to thiabendazole detection be limited to 0.025 μ g/mL.
The present invention select three kinds of carbendazim, benomyl, albendazole thiabendazole analogs verified as chaff interferent into
The selectivity of row thiabendazole sensor.9min is enriched in the methanol solution that thiabendazole and interferent concentration are 4 μ g/mL
Afterwards, it is transferred to progress DPV sweep test in the potassium ferricyanide/potassium ferrocyanide solution, as a result, it has been found that trace electrode is to thiabendazole
Current-responsive be carbendazim, benomyl, 1.51,1.93,2.95 times of current-responsive of albendazole respectively, indicate: the print
Mark sensor has preferable selectivity.Further, on the basis of experimental condition optimization, the same terms are prepared for 5 prints
Apodized electrode measures the thiabendazole standard liquid of 4 μ g/mL, measures 5 times, and the electric current relative standard deviation of electrode response is 4.85%, table
The bright sensor has good reproducibility, and in conjunction with " hole " invertibity on blotting membrane, trace electrode can weigh template molecule
Renaturation uses.Electrode elution, which is placed in 4 DEG C of refrigerator, to be saved, and response after two weeks is down to initial communication value 83% or so,
Show having good stability for sensor.
Embodiment 4
In order to evaluate detection effect of the invention, randomly chooses 9 parts of orange juice solution and carry out thiabendazole content detection and add
Mark recovery experiment.10mL orange juice is taken with graduated cylinder correct amount, 15min is centrifuged under the revolving speed of 4500r/min, then will to be centrifuged solution saturating
It crosses 0.45 μm of filter membrane to be filtered, collects supernatant and be measured.Thiabendazole spiked levels are respectively 1 μ g/mL, 3 μ g/
ML, 5 μ g/mL.It is measured using thiabendazole molecular imprinting electrochemical sensor-differential pulse method.Each sample surveys 3 in parallel
It is secondary.The results are shown in Table 1.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from essence of the invention
In the case where mind and range, other modifications and corrigendum can be made.It is, therefore, intended that including this in appended claims
All such changes and modifications in invention scope.
Claims (7)
1. a kind of preparation method of thiabendazole molecular imprinting electrochemical sensor, it is characterised in that the following steps are included:
(1) modification graphene oxide obtains graphene oxide modified electrode on polishing electrode；
(2) graphene oxide modified electrode is carried out to electroreduction in sodium chloride solution and obtains redox graphene modification electricity
Pole；
(3) in redox graphene modified electrode surface in situ electropolymerization molecularly imprinted polymer, one layer of molecular engram is formed
Film.For molecular engram film using o-phenylenediamine and Resorcino as function monomer, thiabendazole is template molecule；
(4) thiabendazole template molecule is removed, the thiabendazole molecular imprinting electrochemical based on redox graphene is obtained and passes
Sensor.
2. a kind of application method of thiabendazole molecular imprinting electrochemical sensor prepared by claim 1, it is characterised in that packet
Include following steps:
(1) sample solution of suitable volumes, centrifuge separation are measured.The filter membrane that centrifugate crosses 0.45 μm is filtered again, is collected
Supernatant.
(2) thiabendazole content is measured using thiabendazole molecular imprinting electrochemical sensor-differential pulse method.
3. the preparation method of graphene oxide modified electrode according to claim 1, which is characterized in that the polishing electricity
Extremely glass-carbon electrode, graphene oxide modified electrode are added dropwise in polished electrode surface, so by graphene oxide dispersion
It is dried under infrared lamp afterwards obtained；Above-mentioned graphene oxide dispersion is to be dissolved in 10mL deionized water by 10mg graphene oxide
In, ultrasonic disperse 30min is made in centrifuge with the revolving speed centrifugation 5min of 3000r/min.
4. the preparation method of redox graphene modified electrode according to claim 1, which is characterized in that 0.5M's
Method used by electroreduction graphene oxide modified electrode is cyclic voltammetry, reaction condition: in three electricity in sodium chloride solution
Under polar body system, controlling potential range is+0.2V~-1.7V, sweep speed: 50mV/s, scanning circle number: 8 circles.
5. the preparation method of thiabendazole molecular imprinting electrochemical sensor according to claim 1, which is characterized in that
Above-mentioned redox graphene modified electrode surface in situ electropolymerization molecularly imprinted polymer, forms one layer of molecularly imprinted polymer
Method be electrochemical polymerization method.Reaction condition are as follows: electropolymerization liquid be 0.1M PBS, pH=9, cyclic voltammetry condition setting:
Scan current potential: -0.2V~+0.8V；Scanning circle number: 10 circles；Sweep speed: 40mV/s.
6. according to the preparation method of thiabendazole molecular imprinting electrochemical sensor described in patent requirements 1.4, which is characterized in that
The redox graphene modified electrode that thiabendazole molecular engram film is covered with obtained in electropolymerization is immersed to the hydrochloric acid of 0.5M
In solution, elution 10min is stirred at low speed, thiabendazole template molecule is eluted.
7. thiophene benzene miaow prepared by the preparation method of thiabendazole molecular imprinting electrochemical sensor described in claim 1~6
Azoles molecular imprinting electrochemical sensor.
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| CN114479863A (en) * | 2022-01-06 | 2022-05-13 | 中国农业科学院烟草研究所(中国烟草总公司青州烟草研究所) | Carbendazim molecular imprinting ratio type fluorescence sensor and preparation method and application thereof |
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| CN114134529A (en) * | 2021-11-30 | 2022-03-04 | 燕山大学 | Hydrogen evolution electrode and preparation method and application thereof |
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| CN114479863A (en) * | 2022-01-06 | 2022-05-13 | 中国农业科学院烟草研究所(中国烟草总公司青州烟草研究所) | Carbendazim molecular imprinting ratio type fluorescence sensor and preparation method and application thereof |
| CN114479863B (en) * | 2022-01-06 | 2024-01-30 | 中国农业科学院烟草研究所(中国烟草总公司青州烟草研究所) | Carbendazim molecular imprinting ratio type fluorescence sensor and preparation method and application thereof |
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Application publication date: 20181214 |