CN107179348A - A kind of double-template trace electrochemical sensor and its preparation method and application - Google Patents
A kind of double-template trace electrochemical sensor and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of double-template trace electrochemical sensor and its preparation method and application, comprise the following steps：(1) polysulfide violet/glass-carbon electrode is placed in the mixed liquor containing o-phenylenediamine, bensulfuron-methyl and imidacloprid, electropolymerization obtains the electrode of bensulfuron-methyl and imidacloprid modification；(2) electrode for modifying bensulfuron-methyl and imidacloprid soaks in acid solution, elution bensulfuron-methyl and imidacloprid.The present invention constructs a kind of electrochemical sensor based on double-template imprinted polymer, the selective Sensitive Detection of priority for bensulfuron-methyl and imidacloprid, with higher sensitivity, can successively detect bensulfuron-methyl and imidacloprid both target substances simultaneously, and have the advantages that strong antijamming capability, performance stably, cost is low, it is simple to prepare.
Description
Technical field
The present invention relates to electrochemical sensor, in particular it relates to a kind of double-template trace electrochemical sensor and its preparation
Methods and applications.
Background technology
Molecularly imprinted polymer (MIP) has specific recognition to template molecule, it is widely used in template molecule
Detection.MIP has easy preparation, and cost is low, the advantages of stability is good, there is application, such as SPE, chromatogram point in many fields
From preparation with electrochemical sensor etc..MIP electropolymerizations to electrode surface are prepared sensor and can improved to template point by us
The selectivity of son, but be due to the raising that prepared MIP poorly conductives limit transducer sensitivity.Asked to improve this
Topic, increasing nano material be used in the preparation of MIP electrochemical sensors strengthen the sensitivity of sensor.Such as in lead
One layer of MIP and iron/copper metal nano composite material are modified on graptolite electrode ink is used for the inspection of pyridoxol and pyridoxal 5-phosphate salt
Survey, it (is respectively 2.4 × 10 to have relatively low test limit-10mol·L-1With 1.7 × 10-10mol·L-1).MIP/CuO modified electrodes
It is used for dopamine detection, its minimum detectability is 8.0 × 10-9mol·L-1.Answered based on nanoporous leaf type gold and MIP
Electrochemical sensor prepared by condensation material is used to detect metronidazole, and its minimum detectability is 1.8 × 10-11mol·L-1.Graphite
Preparation process of the alkene because being widely used for MIP sensors with excellent electricity, heat and physical property.These biographies reported above
Detection of the sensor to template molecule all shows very high sensitivity.And bimodulus version trace electrochemical sensor has due to it
Can detect two kinds of materials, and sensitivity is high, good selective and be widely used in electroanalysis field.
Bhim et al., which constructs a kind of bimodulus version trace electrochemical sensor, to be used to survey while dopamine and ascorbic acid
It is fixed.Mahavir et al. is prepared a kind of simple with surface imprinted method, and efficient double-template electrochemical sensor is realized pair
Detected while agricultural chemicals glyphosate and glufosinate-ammonium.
Residual agriculture is one of focus of current extensive concern.Bensulfuron-methyl (BSM) is a kind of selective inner sucting conduction type rice field
Herbicide, the features such as with efficient, wide spectrum, low consumption and chronic animals toxicity.In recent years, BSM is in soil, water body, organism
It is wide concerned Deng the residual in matrix and harm.Research shows that BSM can reduce Soil Microorganism quantity and activity, when it
Mass concentration >=100mgL-1When have inhibitory action to embryonic developments such as fish.The BSM detection methods reported at present mainly have height
Effect liquid phase chromatogram method, biological enzyme-linked immunosorbent assay, fluorescence analysis method, MECC and gas chromatography-mass spectrography
Method etc..But these method detection cycles are long, cost is high, and detection range is narrow, so needing to develop, a kind of detection cycle is short, and cost is low
Honest and clean, sensitivity realizes the Sensitive Detection to BSM with selective good electrochemical sensor.
Imidacloprid (IMI) as a kind of new nicotine insecticide, due to its there is hypotoxicity, the advantages of insecticidal activity is high and
It is widely used in agricultural.But harm of residual of the imidacloprid in agricultural product and environment to human body is very big.Therefore, having must
Propose that a kind of selectivity height and the good method of sensitivity carry out the imidacloprid remained in trace detection food or environment.
The content of the invention
In order to make up the deficiency of above research, it is contemplated that the recognition capability of binding molecule imprinted polymer and polysulfide violet
It is electroactive, using bensulfuron-methyl and imidacloprid as template molecule, construct a kind of electrochemistry based on double-template imprinted polymer
Sensor, the selective Sensitive Detection of priority for bensulfuron-methyl and imidacloprid.
To achieve these goals, the invention provides a kind of preparation method of double-template trace electrochemical sensor, bag
Include following steps：(1) polysulfide violet/glass-carbon electrode is placed in the mixed liquor containing o-phenylenediamine, bensulfuron-methyl and imidacloprid, electricity
Polymerization obtains the electrode of bensulfuron-methyl and imidacloprid modification；(2) electrode for modifying bensulfuron-methyl and imidacloprid soaks in acid solution
Bubble, elution bensulfuron-methyl and imidacloprid.
The present invention also provides a kind of double-template trace electrochemical sensor, is prepared into by previously described preparation method
Arrive.
In addition, the present invention also provides one kind according to previously described double-template trace electrochemical sensor in the detection phonetic sulphur of benzyl
Application in grand and imidacloprid.
By above-mentioned technical proposal, the recognition capability of binding molecule imprinted polymer of the present invention is electroactive with polysulfide violet,
A kind of electrochemical sensor based on double-template imprinted polymer is constructed, the priority selectivity for bensulfuron-methyl and imidacloprid
Sensitive Detection, with higher sensitivity, while bensulfuron-methyl and imidacloprid both target substances can be successively detected, and tool
Have the advantages that strong antijamming capability, performance are stable, cost is low, it is simple to prepare.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute a part for specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the scanning electron microscope (SEM) photograph of multi-walled carbon nanotube/glass-carbon electrode；
Fig. 2 is the scanning electron microscope (SEM) photograph of polysulfide violet/multi-walled carbon nanotube/glass-carbon electrode；
Fig. 3 is that double-template molecularly imprinted polymer/polysulfide violet/multi-walled carbon nanotube/glass-carbon electrode prepared by embodiment 1 is swept
Retouch electron microscope；
Fig. 4 is to detect the cyclic voltammetry curve figure in example 1；
Fig. 5 is to detect the differential pulse curve map in example 1；
Fig. 6 is to detect the linear calibration curve figure in example 2；
Fig. 7 is differential pulse current-responsive figure in detection example 3.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points and any value of disclosed scope are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The invention provides a kind of preparation method of double-template trace electrochemical sensor, comprise the following steps：(1) will be poly-
Thionine/glass-carbon electrode is placed in the mixed liquor containing o-phenylenediamine, bensulfuron-methyl and imidacloprid, electropolymerization obtain bensulfuron-methyl and
The electrode of imidacloprid modification；(2) electrode for modifying bensulfuron-methyl and imidacloprid soaks in acid solution, elution bensulfuron-methyl and pyrrole
Worm quinoline.
In the above-mentioned technical solutions, glass-carbon electrode can have multiple choices, for example, can be glass-carbon electrode or enter
The glass-carbon electrode of the glass-carbon electrode of one step modification, such as functionalized multi-wall carbonnanotubes modification, can be achieved the present invention.Wherein,
Functionalized multi-wall carbonnanotubes modified electrode can be prepared by a variety of methods, for example, glass-carbon electrode is immersed into 0.3-0.8mg
mL-1In multi-walled carbon nanotube suspension, potentiostatic electrodeposition 400 seconds under+1.5~1.9V current potential obtain many wall carbon of carboxylated and received
Mitron modified electrode, multi-walled carbon nanotube has been modified in glassy carbon electrode surface, is improved the electric conductivity of electrode, is increased electrode
In specific surface area, embodiment later, illustrated with functionalized multi-wall carbonnanotubes modified electrode.
In the above-mentioned technical solutions, polysulfide violet/glass-carbon electrode refer to polysulfide violet modification glass-carbon electrode, wherein polysulfide violet/
Glass-carbon electrode can be prepared using a variety of methods, for example, cover a strata in glassy carbon electrode surface by interior circulation voltammetric scan method
Thionine, more specifically, by glass-carbon electrode immerse the phosphate buffer solution containing thionine in, within cyclic voltammetry scan method-
0.4V-+0.4V potential range interior circulation voltammetric scan 20-50 circles, sweep speed is 50-100mVs-1It can obtain polysulfide
Violet/glass-carbon electrode, by the strata thionine conductive film of glassy carbon electrode surface electropolymerization one, can directly produce electrochemical signals,
As electrochemical probe.
In the above-mentioned technical solutions, using bensulfuron-methyl and imidacloprid as double-template molecule, o-phenylenediamine is function monomer system
Standby trace polymerization film.After template molecule bensulfuron-methyl and imidacloprid are eluted, it can be left and template molecule chi in blotting membrane
The trace hole that very little and functional group matches.
In detection process, we first add the template molecule bensulfuron-methyl of electrically inactive, and its own can not produce electrification
Signal is learned, but it is incorporated in in trace hole, block trace hole so that the electron transmission of polysulfide violet is hindered, cause
The reduction of polysulfide violet current signal.When adding electroactive template molecule imidacloprid, it is incorporated in trace hole, a side
The electron transmission of face obstruction probe continues to reduce the current signal of polysulfide violet, on the other hand its own also to occur redox anti-
Current signal should be produced, and with the increase of addition concentration, its own current signal gradually strengthens.So we just construct
A kind of double-template molecular imprinting electrochemical sensor based on probe dye successively detection bensulfuron-methyl and imidacloprid.
By above-mentioned technical proposal, the recognition capability of binding molecule imprinted polymer of the present invention is electroactive with polysulfide violet,
A kind of electrochemical sensor based on double-template imprinted polymer is constructed, the priority selectivity for bensulfuron-methyl and imidacloprid
Sensitive Detection, with higher sensitivity, while two kinds of target substances can be successively detected, and with strong antijamming capability, property
Can it is stable, cost is low, the advantages of prepare simple.
In the above-mentioned technical solutions, the amount of the addition of phenylenediamine, bensulfuron-methyl and imidacloprid can have multiple choices, in order to
Prepare higher sensitivity and the stable double-template trace electrochemical sensor of performance, it is preferable that in step (1), adjacent benzene two
The ratio between amine, bensulfuron-methyl, amount of material of imidacloprid are： 10:1~3:2~4.
In the above-mentioned technical solutions, the amount of the addition of phenylenediamine, bensulfuron-methyl and imidacloprid can have multiple choices, in order to
Prepare higher sensitivity and the stable double-template trace electrochemical sensor of performance, it is preferable that in step (1), relative to
1L mixed liquor, the concentration of o-phenylenediamine is 8~12mmolL-1, the concentration of bensulfuron-methyl is 1~3mmolL-1, imidacloprid
Concentration be 2~4mmolL-1。
In above-mentioned technical proposal, the pH of mixed liquor can be selected in relative broad range, in order to prepare higher sensitivity and
The stable double-template trace electrochemical sensor of performance, it is preferable that the pH value of mixed liquor is 4~8.
In above-mentioned technical proposal, mixed liquor can be selected from multi-solvents or buffer solution, higher in order to prepare
Sensitivity and the stable double-template trace electrochemical sensor of performance, it is preferable that mixed liquor includes phosphate buffer and acetonitrile.
In the above-mentioned technical solutions, the proportioning of phosphate buffer and acetonitrile can have multiple choices, higher in order to prepare
Sensitivity and the stable double-template trace electrochemical sensor of performance, it is preferable that the volume ratio of phosphate buffer and acetonitrile
For 3:1.5~2.5.
In the above-mentioned technical solutions, the concentration of phosphate buffer can be selected in relative broad range, in order to prepare
The stable double-template trace electrochemical sensor of higher sensitivity and performance, it is preferable that the concentration of phosphate buffer is
0.08~0.12molL-1。
In the above-mentioned technical solutions, current potential being polymerize in electropolymerization can select in relative broad range, higher in order to prepare
Sensitivity and the stable double-template trace electrochemical sensor of performance, it is preferable that polymerization current potential is -0.4V~+0.8V.
In the above-mentioned technical solutions, current potential being polymerize in electropolymerization can select in relative broad range, higher in order to prepare
Sensitivity and the stable double-template trace electrochemical sensor of performance, it is preferable that
In the above-mentioned technical solutions, sweep speed can be selected in relative broad range in electropolymerization, higher in order to prepare
Sensitivity and the stable double-template trace electrochemical sensor of performance, it is preferable that sweep speed is 45~55mVs-1。
In the above-mentioned technical solutions, acid solution can be selected in relative broad range, including strong acid solution and weak acid solution, in order to make
Standby higher sensitivity and the stable double-template trace electrochemical sensor of performance, it is preferable that acid solution be hydrochloric acid, sulfuric acid solution,
One or more in salpeter solution.
Further, it is excellent in order to prepare higher sensitivity and the stable double-template trace electrochemical sensor of performance
Selection of land, acid solution is hydrochloric acid.
In the above-mentioned technical solutions, soak time can be selected in relative broad range, in order to prepare higher sensitivity and property
The stable double-template trace electrochemical sensor of energy, it is preferable that soak time is 10~20min.
In the above-mentioned technical solutions, the concentration of acid solution can be selected in relative broad range, in order to prepare higher sensitivity and
The stable double-template trace electrochemical sensor of performance, it is preferable that in step (2), in acid solution hydrionic concentration be 0.30~
0.70mol·L-1。
The present invention also provides a kind of double-template trace electrochemical sensor, is prepared into by previously described preparation method
Arrive.
By above-mentioned technical proposal, the recognition capability of binding molecule imprinted polymer of the present invention is electroactive with polysulfide violet,
A kind of electrochemical sensor based on double-template imprinted polymer is constructed, the priority selectivity for bensulfuron-methyl and imidacloprid
Sensitive Detection, with higher sensitivity, while two kinds of target substances can be successively detected, and with strong antijamming capability, property
Can it is stable, cost is low, the advantages of prepare simple.
In addition, the present invention also provides one kind according to previously described double-template trace electrochemical sensor in the detection phonetic sulphur of benzyl
Application in grand and imidacloprid.The double-template trace electrochemical sensor provided using the present invention can the selective Sensitive Detection of priority
The bensulfuron-methyl and imidacloprid gone out in solution, with higher sensitivity, while strong antijamming capability, performance are stable.In detection
During, the template molecule bensulfuron-methyl of electrically inactive is first added, its own can not produce electrochemical signals, but it is incorporated in
In trace hole, trace hole is blocked so that the electron transmission of polysulfide violet is hindered, causes the drop of polysulfide violet current signal
It is low.When adding electroactive template molecule imidacloprid, it is incorporated in trace hole, and on the one hand the electronics of obstruction probe is passed
Pass and continue to reduce the current signal of polysulfide violet, on the other hand its own can also occur redox reaction generation current signal, and
And its own current signal gradually strengthens with the increase of addition concentration.Thus construct a kind of based on probe dye successively inspection
Survey the double-template molecular imprinting electrochemical sensor of agricultural chemicals bensulfuron-methyl and imidacloprid.And for the inspection of bensulfuron-methyl and imidacloprid
Survey be respectively adopted be mono signal (| Δ iPolysulfide violet|) and dual signal (| Δ iImidacloprid|+|ΔiPolysulfide violet|) determine strategy.
The present invention will be described in detail by way of examples below.In following examples, polysulfide violet/glass-carbon electrode is poly-
Thionine/multi-walled carbon nanotube/glass-carbon electrode, preparation method is shown in preparation example 1.
Instrument：CHI830C electrochemical workstations are purchased from Shanghai Chen Hua instrument company, use three-electrode system, glass-carbon electrode
As working electrode, platinum electrode is as auxiliary electrode, and saturated calomel electrode is reference electrode；PHS-3CT type acidometers are purchased from
Shanghai great Pu Instrument Ltd.；KQ-50B ultrasonic disperses instrument is purchased from Kunshan Ultrasonic Instruments Co., Ltd.；Scanning electron microscopy
Mirror model SEM, HitachiS-4800,10kV；Multi-walled carbon nanotube is purchased from Nanjing pioneer Nanosolutions GmbH；Thionine
Purchased from SIGMA-ALDRICH reagents Co., Ltd, China；O-phenylenediamine is purchased from SIGMA-ALDRICH reagents Co., Ltd, in
State；Bensulfuron-methyl, Garagard, pyrazosulfuron, imidacloprid, thiacloprid and Acker safe (thiacloprid M) are purchased from Shanghai Ling Feng chemistry examinations
Agent Co., Ltd, other are conventional commercial product.
Preparation example 1
The multi-walled carbon nanotube for weighing 2.5mg carboxylated is put into 5mL redistilled waters ultrasonic half an hour and obtains 0.5mg
mL-1Multi-walled carbon nanotube black suspension.Glass-carbon electrode after processing is immersed in this suspension, it is permanent under+1.7V current potential
Potential deposition 400 seconds, obtains functionalized multi-wall carbonnanotubes modified electrode；
Multi-walled carbon nanotube/glass-carbon electrode is placed in 5mL, 5mmolL-1In thionine (PBS, pH6.0) solution, using following
Modified electrode is made in ring voltammetry electropolymerization, and polymerization current potential is -0.4V-+0.4V, and the polymerization number of turns is 30 circles, and it is 50mV to sweep speed
s-1, you can polysulfide violet/Multiwalled Carbon Nanotubes Modified Electrode is made.
Functionalized multi-wall carbonnanotubes modified electrode and polysulfide violet/multi-walled carbon nanotube are repaiied by SEM
The surface topography of decorations electrode is characterized, and sees Fig. 1 and Fig. 2.Multi-walled carbon nanotube is electrically deposited after glassy carbon electrode surface, is such as schemed
Shown in 1, obvious tridimensional network is showed, it not only increases the electric conductivity of electrode, and significantly increases electrode
Specific surface area.
After electropolymerization thionine, as shown in Fig. 2 multi-walled carbon nanotube/glassy carbon electrode surface, which can be observed, covers one layer uniformly
Laminar film, this shows that polysulfide violet has been modified multi-walled carbon nanotube/glassy carbon electrode surface.
Embodiment 1
Polysulfide violet/multi-walled carbon nanotube/glass-carbon electrode is placed in containing o-phenylenediamine 10mmolL-1, bensulfuron-methyl
2mmol·L-1, imidacloprid 3mmolL-13mL concentration be 0.10molL-1Phosphate buffer solution (PBS, pH=6.0) and
In 2mL acetonitrile mixed polymerization liquid, modified electrode is obtained using electropolymerization, polymerization current potential is -0.4V-+0.8V, and the polymerization number of turns is 20
Circle, it is 50mVs to sweep speed-1.The modified electrode is then placed in 0.50molL-1The 15 minutes elution phonetic sulphur of benzyl is soaked in hydrochloric acid
Grand and imidacloprid, is cleaned with redistilled water and produces double-template molecularly imprinted polymer/polysulfide violet/multi-walled carbon nanotube/glass carbon
Electrode.
By SEM to double-template molecularly imprinted polymer/polysulfide violet/multi-walled carbon nanotube/glass carbon electricity
The surface topography of pole is characterized, and sees Fig. 3.Compared with Fig. 1, Fig. 2, double-template molecularly imprinted polymer/polysulfide violet/many walls carbon is received
The surface of mitron/glass-carbon electrode becomes more coarse, as shown in figure 3, illustrate successfully to prepare double-template molecularly imprinted polymer/
Polysulfide violet/multi-walled carbon nanotube/glass-carbon electrode.
Embodiment 2
Polysulfide violet/multi-walled carbon nanotube/glass-carbon electrode is placed in containing o-phenylenediamine 8mmolL-1, bensulfuron-methyl
1mmol·L-1, imidacloprid 1mmolL-13mL concentration be 0.08molL-1Phosphate buffer solution (PBS, pH=4.0)
In 1.5mL acetonitrile mixed polymerization liquid, modified electrode is obtained using electropolymerization, polymerization current potential is -0.4V-+0.8V, polymerize the number of turns
For 10 circles, it is 45mVs to sweep speed-1.The modified electrode is then placed in 0.30molL-110 minutes elution benzyls are soaked in hydrochloric acid
Sulfometuron Methyl and imidacloprid, with redistilled water clean produce double-template molecularly imprinted polymer/polysulfide violet/multi-walled carbon nanotube/
Glass-carbon electrode.
Embodiment 3
Polysulfide violet/multi-walled carbon nanotube/glass-carbon electrode is placed in containing o-phenylenediamine 12mmolL-1, bensulfuron-methyl
5mmol·L-1, imidacloprid 5mmolL-13mL concentration be 0.12molL-1Phosphate buffer solution (PBS, pH=8.0) and
In 2.5mL acetonitrile mixed polymerization liquid, modified electrode is obtained using electropolymerization, polymerization current potential is -0.4V-+0.8V, and the polymerization number of turns is
50 circles, it is 55mVs to sweep speed-1.The modified electrode is then placed in 0.70molL-120 minutes elution benzyls are soaked in hydrochloric acid phonetic
Sulphur is grand and imidacloprid, is cleaned with redistilled water and produces double-template molecularly imprinted polymer/polysulfide violet/multi-walled carbon nanotube/glass
Carbon electrode.
Reference examples 1
Method according to embodiment 1 prepares non-trace electrode, unlike, without bensulfuron-methyl and imidacloprid.
Detect example 1：Electrochemical Characterization
The electrode prepared in the electrode prepared in embodiment 1, embodiment 1 is recorded in conjunction with 5 × 10-6mol·L-1BSM、
The electrode prepared in embodiment 1 is in conjunction with 1 × 10-5mol·L-1IMI cyclic voltammetry curve, respectively curve a in corresponding diagram 4,
b、c；The cyclic voltammetry curve of the electrode prepared in reference examples 1 is recorded under the same terms, respectively curve d, e, f in corresponding diagram 4；
The electrode prepared in the electrode prepared in embodiment 1, embodiment 1 is recorded in conjunction with 5 × 10-6mol·L-1BSM、
The electrode prepared in embodiment 1 is in conjunction with 1 × 10-5mol·L-1IMI differential pulse curve, respectively curve a in corresponding diagram 5,
b、c；The differential pulse curve of the electrode prepared in reference examples 1 is recorded under the same terms, respectively curve d, e, f in corresponding diagram 5.
As shown in Figure 4, Figure 5, the electrode prepared in embodiment 1 is after i.e. template molecule bensulfuron-methyl and imidacloprid are eluted,
A pair of reversible redox peaks of polysulfide violet are occurred in that at -0.38V and -0.42V.When the addition 5.0 × 10 into blank bottom liquid- 6mol·L-1After bensulfuron-methyl, the current signal of polysulfide violet decreases.When the addition 1.0 × 10 into above-mentioned solution-5mol·L-1After imidacloprid, it has been found that the electric signal of polysulfide violet further reduce and occurred in that at -0.94V one it is irreversible also
Parent peak.This explanation mono signal (| Δ iPolysulfide violet|) detection bensulfuron-methyl and dual signal (| Δ iImidacloprid|+|ΔiPolysulfide violet|) determine imidacloprid
It is tactful practical.
Such as shown in Figure 4, Figure 5, when the electrode prepared in reference examples 1 does not have trace cave, it is impossible to reference to bensulfuron-methyl and pyrrole
Worm quinoline molecule, while the electron transfer pathways also without polysulfide violet.Therefore, the characteristic peak of polysulfide violet and imidacloprid does not all go out
It is existing.
Detect example 2：Linearity test
The electrode prepared in record embodiment 1 is 1.0 × 10 being continuously added to bensulfuron-methyl concentration-8mol/L、5.0×10-8mol/L、1.0×10-7mol/L、5.0×10-7mol/L、1.0×10-6mol/L、4.0×10-6mol/L、 6.0×10- 6mol/L、1.0×10-5Mol/L differential pulse curve；It is 1.0 × 10 to be continuously added to imidacloprid concentration-7mol/L、5.0×
10-7mol/L、1.0×10-6mol/L、5.0×10-6mol/L、1.0×10-5mol/L、 4.0×10-5mol/L、6.0×10- 5mol/L、1.0×10-4mol·L-1Differential pulse curve, and record the electrode that is prepared in embodiment 1 and adding various concentrations
Bensulfuron-methyl and imidacloprid caused by curent change, draw calibration curve, as shown in Figure 6.
It is 1.0 × 10 that concentration is added into blank PBS solution-8mol·L-1-1.0×10-5mol·L-1Bensulfuron-methyl,
The i in concentration rangePolysulfide violetWith cBensulfuron-methylIt is directly proportional, equation of linear regression is Δ ia=1.199e-6+1.652ca(μM) (R=
0.9963), detection is limited to 7.8 × 10-9mol·L-1(S/N=3) (see Fig. 6).
Again using concentration as 1.0 × 10-5mol·L-1Bensulfuron-methyl solution in polysulfide violet reduction peak current value on the basis of,
Dual signal absolute value sum that imidacloprid and polysulfide violet are constituted (| Δ iImidacloprid|+|ΔiPolysulfide violet|) with imidacloprid concentration 1.0 ×
10-7~1.0 × 10-4mol·L-1In the range of it is proportional, equation of linear regression is Δ ib(μ A)=| Δ iImidacloprid|+|ΔiPolysulfide violet|
=5.652e-7+0.1592cImidacloprid(μM) (R=0.9987), detection is limited to 6.5 × 10-8Mol/L (S/N=3) (see Fig. 6).
Detect example 3：Selectivity
Garagard (TB), pyrazosulfuron (PSE) are selected as the chaff interference of bensulfuron-methyl；Thiacloprid (THI), Acker are safe
(THIM) as the chaff interference of imidacloprid, the structural formula of bensulfuron-methyl and imidacloprid, which is seen below in text, record record embodiment 1, to be prepared
Electrode and reference examples 1 in the electrode for preparing respectively in conjunction with 1.0 × 10-5mol·L-1Bensulfuron-methyl, 5.0 × 10- 5mol·L-1The differential pulse current-responsive figure of imidacloprid and other chaff interferences.
As shown in fig. 7, the electrode prepared in embodiment 1 is bright for the current-responsive of template molecule bensulfuron-methyl and imidacloprid
It is aobvious to be higher than chaff interference.
Detect example 4：Repeatability, reproducibility and stability
5 electrodes are prepared for using the method for embodiment 1,5.0 × 10 are detected with differential pulse voltametry-6mol·L-1
Bensulfuron-methyl, obtains five groups of response current values, and relative standard deviation (RSD) is 3.6%；Detection 5.0 × 10-5mol·L-1Pyrrole
Worm quinoline obtains five groups of response current values, and relative standard deviation (RSD) is 4.5%, shows that the sensor prepared has good weight
Renaturation.
Electrode prepared by the method for same embodiment 1 is eluted in conjunction with being repeated 5 times, detect 5.0 × 10- 6mol·L-1Bensulfuron-methyl and 5.0 × 10-5mol·L-1Imidacloprid, obtained relative standard deviation (RSD) is respectively 3.8%
With 4.7%, show that prepared sensor has good reproducibility.
Prepared modified electrode is placed at 4 DEG C and preserved, detected every three days with differential pulse voltametry its to 5.0 ×
10-6mol·L-1Bensulfuron-methyl and 5.0 × 10-5mol·L-1The response current of imidacloprid, the electrode is still kept just after finding two weeks
The 94.5% of beginning electric current and 92.1%, show that the sensor prepared has good stability.
Detect example 5：Actual sample is detected
What selection paddy field water evaluated the sensor that is prepared in embodiment 1, embodiment 2, embodiment 3 as actual sample should
Use ability.Actual sample process step is as follows：2mL paddy field waters are taken to be put into supercentrifuge centrifugation half under 4000rpm rotating speeds small
When, take supernatant liquor pH=5.0,0.1molL-1PBS to be diluted to 5mL, detected using standard addition method.As a result such as
Shown in table 1, the rate of recovery is between 94.6%-104.5%, and relative standard deviation shows the electrification in 2.0%-4.8%
The detection of bensulfuron-methyl and imidacloprid in actual water sample can be used for by learning sensor.
The computational methods of the rate of recovery：The rate of recovery=sensor detection limit/addition × 100%
Table 1
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of preparation method of double-template trace electrochemical sensor, it is characterised in that comprise the following steps：
(1) polysulfide violet/glass-carbon electrode is placed in the mixed liquor containing o-phenylenediamine, bensulfuron-methyl and imidacloprid, electropolymerization is obtained
The electrode modified to bensulfuron-methyl and imidacloprid；
(2) electrode for modifying bensulfuron-methyl and imidacloprid soaks in acid solution, elution bensulfuron-methyl and imidacloprid.
2. preparation method according to claim 1, wherein, in step (1), o-phenylenediamine, bensulfuron-methyl, imidacloprid
The ratio between amount of material is：10:1~3:2~4.
3. preparation method according to claim 1, wherein, in step (1), the mixed liquor relative to 1L, o-phenylenediamine
Concentration be 8~12mmolL-1, the concentration of bensulfuron-methyl is 1~3mmolL-1, the concentration of imidacloprid is 2~4mmolL-1。
4. preparation method according to claim 1, wherein, in step (1), the pH value of mixed liquor is 4~8.
5. preparation method according to claim 4, wherein, mixed liquor includes phosphate buffer and acetonitrile；Preferably, phosphorus
The volume ratio of phthalate buffer and acetonitrile is 3:1.5~2.5；And/or, the concentration of phosphate buffer for 0.08~
0.12mol·L-1。
6. preparation method according to claim 1, wherein, the condition of electropolymerization is at least met with the next item down：It polymerize current potential
For -0.4V~+0.8V；It is 10~50 circles to polymerize the number of turns；Sweep speed is 45~55mVs-1。
7. preparation method according to claim 1, wherein, in step (2), acid solution is that hydrochloric acid, sulfuric acid solution and nitric acid are molten
One or more in liquid；And/or, soak time is 10~20min.
8. preparation method according to claim 7, wherein, in step (2), in acid solution hydrionic concentration be 0.30~
0.70mol·L-1；
Preferably, acid solution is hydrochloric acid.
9. a kind of double-template trace electrochemical sensor, it is characterised in that pass through the preparation side described in claim any one of 1-8
Method is prepared.
10. double-template trace electrochemical sensor according to claim 9 answering in detection bensulfuron-methyl and imidacloprid
With.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108693229A (en) * | 2018-05-22 | 2018-10-23 | 上海市农业科学院 | A kind of molecular imprinting electrochemical sensor and preparation method for detecting patulin |
| CN109900766A (en) * | 2019-02-22 | 2019-06-18 | 安徽师范大学 | Dual signal molecular imprinting electrochemical sensor and its preparation method and application |
| CN110511423A (en) * | 2019-08-08 | 2019-11-29 | 江南大学 | The method that double-template molecularly imprinted material on surface removes imidacloprid and Acetamiprid in water-soluble tea extract simultaneously |
| CN113702453A (en) * | 2021-06-03 | 2021-11-26 | 江苏大学 | AuNPs-p-Ti3C2TxComposite material and preparation method and application thereof |
| CN114609202A (en) * | 2022-03-08 | 2022-06-10 | 深圳职业技术学院 | PIP/Ti3C2TxPreparation method of R/GCE electrochemical sensor and LM detection method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105223258A (en) * | 2015-09-22 | 2016-01-06 | 江苏大学 | Amikacin and streptomysin double-template molecularly imprinted solid phase extraction column and using method |
| CN105233809A (en) * | 2015-09-22 | 2016-01-13 | 江苏大学 | Double-template molecularly-imprinted solid-phase extraction column and application method |
-
2017
- 2017-06-21 CN CN201710473408.4A patent/CN107179348B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105223258A (en) * | 2015-09-22 | 2016-01-06 | 江苏大学 | Amikacin and streptomysin double-template molecularly imprinted solid phase extraction column and using method |
| CN105233809A (en) * | 2015-09-22 | 2016-01-13 | 江苏大学 | Double-template molecularly-imprinted solid-phase extraction column and application method |
Non-Patent Citations (3)
| Title |
|---|
| BHIM BALI PRASAD等: "A dual-template imprinted polymer-modified carbon ceramic electrode for ultra trace simultaneous analysis of ascorbic acid and dopamine", 《BIOSENSORS AND BIOELECTRONICS》 * |
| JUNQING FU等: "Current status and challenges of ion imprinting", 《J. MATER. CHEM. A》 * |
| ZHIGANG XU等: "Development of dual-templates molecularly imprinted stir barsorptive extraction and its application for the analysis ofenvironmental estrogens in water and plastic samples", 《JOURNAL OF CHROMATOGRAPHY A》 * |
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| CN108693229B (en) * | 2018-05-22 | 2019-11-15 | 上海市农业科学院 | It is a kind of for detecting the molecular imprinting electrochemical sensor and preparation method of patulin |
| CN109900766A (en) * | 2019-02-22 | 2019-06-18 | 安徽师范大学 | Dual signal molecular imprinting electrochemical sensor and its preparation method and application |
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| CN115184431B (en) * | 2022-07-26 | 2024-03-12 | 常州大学 | Preparation method and application of molecular imprinting electrochemical sensor with double-signal probe strategy |
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