CN107179348B - 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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- CN107179348B CN107179348B CN201710473408.4A CN201710473408A CN107179348B CN 107179348 B CN107179348 B CN 107179348B CN 201710473408 A CN201710473408 A CN 201710473408A CN 107179348 B CN107179348 B CN 107179348B
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- imidacloprid
- bensulfuron
- methyl
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000005906 Imidacloprid Substances 0.000 claims abstract description 75
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229940056881 imidacloprid Drugs 0.000 claims abstract description 68
- 239000005472 Bensulfuron methyl Substances 0.000 claims abstract description 61
- XMQFTWRPUQYINF-UHFFFAOYSA-N bensulfuron-methyl Chemical group COC(=O)C1=CC=CC=C1CS(=O)(=O)NC(=O)NC1=NC(OC)=CC(OC)=N1 XMQFTWRPUQYINF-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000005077 polysulfide Substances 0.000 claims abstract description 45
- 229920001021 polysulfide Polymers 0.000 claims abstract description 37
- 150000008117 polysulfides Polymers 0.000 claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 32
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 238000001514 detection method Methods 0.000 claims description 23
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000008363 phosphate buffer Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical compound Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 24
- 229920000642 polymer Polymers 0.000 abstract description 9
- 238000011896 sensitive detection Methods 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 6
- 239000013076 target substance Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 31
- 239000002048 multi walled nanotube Substances 0.000 description 29
- 229920000344 molecularly imprinted polymer Polymers 0.000 description 17
- 239000000523 sample Substances 0.000 description 9
- KUUVQVSHGLHAKZ-UHFFFAOYSA-N thionine Chemical compound C=1C=CC=CSC=CC=1 KUUVQVSHGLHAKZ-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 229910021397 glassy carbon Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 4
- 239000008055 phosphate buffer solution Substances 0.000 description 4
- 238000010408 sweeping Methods 0.000 description 4
- HOKKPVIRMVDYPB-UVTDQMKNSA-N (Z)-thiacloprid Chemical compound C1=NC(Cl)=CC=C1CN1C(=N/C#N)/SCC1 HOKKPVIRMVDYPB-UVTDQMKNSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 239000005940 Thiacloprid Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000004832 voltammetry Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- UQQCAXMSWRLMQP-UHFFFAOYSA-N Cl.[S] Chemical compound Cl.[S] UQQCAXMSWRLMQP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VXMNDQDDWDDKOQ-UHFFFAOYSA-N Pyrazosulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2N(N=CC=2C(O)=O)C)=N1 VXMNDQDDWDDKOQ-UHFFFAOYSA-N 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229960003638 dopamine Drugs 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000012417 linear regression Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 1
- ZBMRKNMTMPPMMK-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid;azane Chemical compound [NH4+].CP(O)(=O)CCC(N)C([O-])=O ZBMRKNMTMPPMMK-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000002965 ELISA Methods 0.000 description 1
- 239000005562 Glyphosate Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000013020 embryo development Effects 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 229940097068 glyphosate Drugs 0.000 description 1
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 description 1
- 229960000282 metronidazole Drugs 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229960002715 nicotine Drugs 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- NGVDGCNFYWLIFO-UHFFFAOYSA-N pyridoxal 5'-phosphate Chemical class CC1=NC=C(COP(O)(O)=O)C(C=O)=C1O NGVDGCNFYWLIFO-UHFFFAOYSA-N 0.000 description 1
- LXNHXLLTXMVWPM-UHFFFAOYSA-N pyridoxine Chemical compound CC1=NC=C(CO)C(CO)=C1O LXNHXLLTXMVWPM-UHFFFAOYSA-N 0.000 description 1
- 235000008160 pyridoxine Nutrition 0.000 description 1
- 239000011677 pyridoxine Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 101150054688 thiM gene Proteins 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
The invention discloses a kind of double-template trace electrochemical sensors and its preparation method and application, the following steps are included: polysulfide violet/glass-carbon electrode is placed in the mixed liquor containing o-phenylenediamine, bensulfuron-methyl and imidacloprid by (1), electropolymerization obtains the electrode of bensulfuron-methyl and imidacloprid modification；(2) electrode that bensulfuron-methyl and imidacloprid are modified is impregnated in acid solution, elutes bensulfuron-methyl and imidacloprid.The present invention constructs a kind of electrochemical sensor based on double-template imprinted polymer, successive selective Sensitive Detection for bensulfuron-methyl and imidacloprid, sensitivity with higher, bensulfuron-methyl and imidacloprid both target substances can successively be detected simultaneously, and have many advantages, such as strong antijamming capability, performance it is stable, it is at low cost, prepare it is simple.
Description
Technical field
The present invention relates to electrochemical sensors, and in particular, to a kind of double-template trace electrochemical sensor and its preparation
Methods and applications.
Background technique
Molecularly imprinted polymer (MIP) has specific recognition to template molecule, it is made to be widely used in template molecule
Detection.The advantages that MIP has easily preparation, at low cost, and stability is good, has application in many fields, such as Solid Phase Extraction, chromatography point
From the preparation etc. with electrochemical sensor.MIP electropolymerization to electrode surface is prepared sensor and can improved to template point by we
The selectivity of son, but since prepared MIP poorly conductive limits the raising of transducer sensitivity.It is asked to improve this
Topic, more and more nano materials be used in the preparation of MIP electrochemical sensor enhance the sensitivity of sensor.Such as in lead
One layer of MIP is modified on graptolite electrode ink and iron/copper metal nanocomposite is used for the inspection of pyridoxol and pyridoxal 5-phosphate salt
It surveys, there is lower detection limit (respectively 2.4 × 10-10mol·L-1With 1.7 × 10-10mol·L-1).MIP/CuO modified electrode
It is used for dopamine detection, minimum detectability is 8.0 × 10-9mol·L-1.It is compound based on nanoporous leaf type gold and MIP
Electrochemical sensor prepared by material is 1.8 × 10 for detecting metronidazole, minimum detectability-11mol·L-1.Graphene
Because having excellent electricity, heat and physical property to be widely used for the preparation process of MIP sensor.These sensings reported above
Device all shows very high sensitivity to the detection of template molecule.And bimodulus version trace electrochemical sensor due to its have can
To detect two kinds of substances, and high sensitivity, good selective and be widely used in electroanalysis field.
Survey while Bhim et al. constructs a kind of bimodulus version trace electrochemical sensor for 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 realizes pair
It is detected while pesticide glyphosate and glufosinate-ammonium.
It is one of the hot spot of current extensive concern that agriculture is residual.Bensulfuron-methyl (BSM) is a kind of selective inner sucting conduction type rice field
Herbicide has the characteristics that efficient, wide spectrum, low dosage and chronic animals toxicity.In recent years, BSM is in soil, water body, organism
Residual and harm in equal matrixes are widely noticed.Research shows that BSM can be such that Soil Microorganism quantity and activity reduces, when its matter
Measure concentration >=100mgL-1When have inhibiting effect to embryonic developments such as fish.The BSM detection method reported at present mainly has efficiently
Liquid chromatography, biological enzyme-linked immunosorbent assay, fluorescence analysis method, capillary chromatography and gas chromatography-mass spectrometry
Deng.But these method detection cycles are long, and at high cost, detection range is narrow, so it is short to need to develop a kind of detection cycle, it is at low cost
Honest and clean, sensitivity realizes the Sensitive Detection to BSM with selective good electrochemical sensor.
Imidacloprid (IMI) is used as a kind of novel nicotine insecticide, since it has many advantages, such as hypotoxicity, insecticidal activity it is high and
It is widely used in agricultural.But residual of the imidacloprid in agricultural product and environment is very big to the harm of human body.Therefore, having must
It is proposed that a kind of selectivity is high and the good method of sensitivity carrys out remaining imidacloprid in trace detection food or environment.
Summary of the invention
In order to make up the deficiency of the above research, the present invention is directed to the recognition capabilities 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 successive selective Sensitive Detection for bensulfuron-methyl and imidacloprid.
To achieve the goals above, the present invention provides a kind of preparation method of double-template trace electrochemical sensor, packets
It includes following steps: (1) polysulfide violet/glass-carbon electrode being 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 that bensulfuron-methyl and imidacloprid are modified is soaked in acid solution
Bubble elutes bensulfuron-methyl and imidacloprid.
The present invention also provides a kind of double-template trace electrochemical sensors, are prepared by previously described preparation method
It arrives.
In addition, the present invention also provides a kind of according to previously described double-template trace electrochemical sensor in the detection phonetic sulphur of benzyl
Application in grand and imidacloprid.
Through the above technical solutions, the recognition capability of binding molecule imprinted polymer of the present invention and polysulfide violet is electroactive,
A kind of electrochemical sensor based on double-template imprinted polymer is constructed, the successive selectivity for bensulfuron-methyl and imidacloprid
Sensitive Detection, sensitivity with higher, while bensulfuron-methyl and imidacloprid both target substances can be successively detected, and have
Have the advantages that strong antijamming capability, performance it is stable, it is at low cost, prepare it is simple.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of 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 multi-walled carbon nanotube/glass-carbon electrode scanning electron microscope (SEM) photograph；
Fig. 2 is polysulfide violet/multi-walled carbon nanotube/glass-carbon electrode scanning electron microscope (SEM) photograph；
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 the cyclic voltammetry curve figure detected in example 1；
Fig. 5 is the differential pulse curve graph detected in example 1；
Fig. 6 is the linear calibration curve figure detected in example 2；
Fig. 7 is differential pulse current-responsive figure in detection example 3.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of preparation methods of double-template trace electrochemical sensor, comprising the following steps: (1) will gather
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 that bensulfuron-methyl and imidacloprid are modified is impregnated in acid solution, elutes bensulfuron-methyl and pyrrole
Worm quinoline.
In the above-mentioned technical solutions, glass-carbon electrode such as can be glass-carbon electrode there are many selection, be also possible into
The glass-carbon electrode of one step modification, such as the glass-carbon electrode of 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, such as glass-carbon electrode is immersed 0.3-0.8mg
mL-1In multi-walled carbon nanotube suspension, potentiostatic electrodeposition 400 seconds under the current potential of+1.5~1.9V obtain carboxylated multi wall carbon and receive
Mitron modified electrode has modified multi-walled carbon nanotube in glassy carbon electrode surface, has improved the electric conductivity of electrode, increase electrode
Specific surface area in embodiment later, is 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, such as cover a strata in glassy carbon electrode surface by interior cyclic voltammetry scan method
Thionine, more specifically, by glass-carbon electrode immerse the phosphate buffer solution containing thionine in, within cyclic voltammetry scan method-
Cyclic voltammetry scan 20-50 is enclosed in the potential range of 0.4V-+0.4V, scanning speed 50-100mVs-1Polysulfide can be obtained
Violet/glass-carbon electrode, by can directly generate electrochemical signals in one strata thionine conductive film of glassy carbon electrode surface electropolymerization,
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 in blotting membrane and template molecule ruler
The trace hole that very little and functional group matches.
In the detection process, the template molecule bensulfuron-methyl of electrically inactive is first added in we, its own cannot generate electrification
Signal is learned, but it is incorporated in in trace hole, blocks trace hole and 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, and on the other hand it is anti-also redox to occur in its own
Current signal should be generated, and its own current signal gradually increases with the increase of addition concentration.We just construct in this way
A kind of double-template molecular imprinting electrochemical sensor successively detecting bensulfuron-methyl and imidacloprid based on probe dye.
Through the above technical solutions, the recognition capability of binding molecule imprinted polymer of the present invention and polysulfide violet is electroactive,
A kind of electrochemical sensor based on double-template imprinted polymer is constructed, the successive selectivity for bensulfuron-methyl and imidacloprid
Sensitive Detection, sensitivity with higher, while two kinds of target substances can be successively detected, and there is strong antijamming capability, property
Energy is stable, at low cost, prepares the advantages that simple.
In the above-mentioned technical solutions, the amount of the addition of phenylenediamine, bensulfuron-methyl and imidacloprid can there are many selection, 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 substance of imidacloprid are as follows: 10:1~3:2~4.
In the above-mentioned technical solutions, the amount of the addition of phenylenediamine, bensulfuron-methyl and imidacloprid can there are many selection, 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
The mixed liquor of 1L, the concentration of o-phenylenediamine are 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 a wider 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, 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 proportion of phosphate buffer and acetonitrile can be higher in order to prepare there are many selection
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 a wider range, in order to prepare
Higher sensitivity and the stable double-template trace electrochemical sensor of 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 a wider 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 a wider 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, scanning speed can select in a wider range in electropolymerization, higher in order to prepare
Sensitivity and the stable double-template trace electrochemical sensor of performance, it is preferable that scanning speed is 45~55mVs-1。
In the above-mentioned technical solutions, acid solution can select in a wider 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 of nitric acid solution is a variety of.
Further, excellent in order to prepare higher sensitivity and the stable double-template trace electrochemical sensor of performance
Selection of land, acid solution are hydrochloric acid.
In the above-mentioned technical solutions, soaking time can select in a wider range, in order to prepare higher sensitivity and property
The stable double-template trace electrochemical sensor of energy, it is preferable that soaking time is 10~20min.
In the above-mentioned technical solutions, the concentration of acid solution can select in a wider 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 sensors, are prepared by previously described preparation method
It arrives.
Through the above technical solutions, the recognition capability of binding molecule imprinted polymer of the present invention and polysulfide violet is electroactive,
A kind of electrochemical sensor based on double-template imprinted polymer is constructed, the successive selectivity for bensulfuron-methyl and imidacloprid
Sensitive Detection, sensitivity with higher, while two kinds of target substances can be successively detected, and there is strong antijamming capability, property
Energy is stable, at low cost, prepares the advantages that simple.
In addition, the present invention also provides a kind of according to previously described double-template trace electrochemical sensor in the detection phonetic sulphur of benzyl
Application in grand and imidacloprid.It can successive selective Sensitive Detection using double-template trace electrochemical sensor provided by the invention
Bensulfuron-methyl and imidacloprid in solution out, sensitivity with higher, while strong antijamming capability, performance are stablized.It is detecting
In the process, the template molecule bensulfuron-methyl of electrically inactive is first added, its own cannot generate electrochemical signals, but it is incorporated in
In trace hole, blocks trace hole and the electron transmission of polysulfide violet is hindered, lead to the drop of polysulfide violet current signal
It is low.When adding electroactive template molecule imidacloprid, it is incorporated in trace hole, and the electronics on the one hand blocking probe passes
The current signal for continuing to reduce polysulfide violet is passed, on the other hand redox reaction generation current signal can also occurs in its own, and
And its own current signal gradually increases with the increase of addition concentration.One kind is thus constructed successively to examine based on probe dye
Survey the double-template molecular imprinting electrochemical sensor of pesticide bensulfuron-methyl and imidacloprid.And the inspection for bensulfuron-methyl and imidacloprid
Survey be respectively adopted be mono signal (| Δ iPolysulfide violet|) and dual signal (| Δ iImidacloprid|+|ΔiPolysulfide violet|) measurement strategy.
The present invention will be described in detail by way of examples below.In following embodiment, polysulfide violet/glass-carbon electrode is poly-
Thionine/multi-walled carbon nanotube/glass-carbon electrode, preparation method are shown in preparation example 1.
Instrument: CHI830C electrochemical workstation is purchased from Shanghai Chen Hua instrument company, uses three-electrode system, glass-carbon electrode
As working electrode, for platinum electrode as auxiliary electrode, saturated calomel electrode is reference electrode；PHS-3CT type acidometer is purchased from
Shanghai great Pu Instrument Ltd.；KQ-50B ultrasonic disperse 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 reagent Co., Ltd, China；O-phenylenediamine is purchased from SIGMA-ALDRICH reagent Co., Ltd, in
State；Bensulfuron-methyl, Garagard, pyrazosulfuron, imidacloprid, thiacloprid and Acker safe (thiacloprid M) are tried purchased from Shanghai Ling Feng chemistry
Agent Co., Ltd, other are conventional commercial products.
Preparation example 1
The multi-walled carbon nanotube for weighing 2.5mg carboxylated is put into 5mL secondary distilled water ultrasonic half an hour and obtains 0.5mg
mL-1Multi-walled carbon nanotube black suspension.By treated, glass-carbon electrode immerses in this suspension, permanent under the current potential of+1.7V
Potential deposition 400 seconds, obtain 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 polymerization circle number is 30 circles, and sweeping speed is 50mV
s-1, can be prepared by polysulfide violet/Multiwalled Carbon Nanotubes Modified Electrode.
Functionalized multi-wall carbonnanotubes modified electrode and polysulfide violet/multi-walled carbon nanotube are repaired by scanning electron microscope
The surface topography of decorations electrode is characterized, and sees Fig. 1 and Fig. 2.After multi-walled carbon nanotube is electrically deposited glassy carbon electrode surface, such as scheme
Shown in 1, apparent 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 polymerization circle number is 20
Circle, sweeping speed is 50mVs-1.The modified electrode is then placed in 0.50molL-1The 15 minutes phonetic sulphur of elution benzyl is impregnated in hydrochloric acid
Grand and imidacloprid is cleaned with secondary distilled water up to double-template molecularly imprinted polymer/polysulfide violet/multi-walled carbon nanotube/glass carbon
Electrode.
By scanning electron microscope to double-template molecularly imprinted polymer/polysulfide violet/multi-walled carbon nanotube/glass-carbon electrode
Surface topography characterized, see Fig. 3.Compared with Fig. 1, Fig. 2, double-template molecularly imprinted polymer/polysulfide violet/multi-wall carbon nano-tube
Pipe/glass-carbon electrode surface becomes more coarse, as shown in figure 3, illustrating successfully to prepare double-template molecularly imprinted polymer/poly-
Thionine/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) and
In 1.5mL acetonitrile mixed polymerization liquid, modified electrode is obtained using electropolymerization, polymerization current potential is -0.4V-+0.8V, and polymerization circle number is
10 circles, sweeping speed is 45mVs-1.The modified electrode is then placed in 0.30molL-1It is phonetic that 10 minutes elution benzyls are impregnated in hydrochloric acid
Sulphur is grand and imidacloprid, is cleaned with secondary distilled water up to 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 polymerization circle number is
50 circles, sweeping speed is 55mVs-1.The modified electrode is then placed in 0.70molL-1It is phonetic that 20 minutes elution benzyls are impregnated in hydrochloric acid
Sulphur is grand and imidacloprid, is cleaned with secondary distilled water up to double-template molecularly imprinted polymer/polysulfide violet/multi-walled carbon nanotube/glass
Carbon electrode.
Reference examples 1
Non- trace electrode is prepared according to the method for embodiment 1, unlike, do not add bensulfuron-methyl and imidacloprid.
Detect example 1: electrochemical Characterization
The electrode for preparing in record embodiment 1, the electrode prepared in embodiment 1 are in conjunction with 5 × 10-6mol·L-1BSM, reality
The electrode prepared in example 1 is applied in conjunction with 1 × 10-5mol·L-1The cyclic voltammetry curve of IMI, respectively correspond curve a, b in Fig. 4,
c；The cyclic voltammetry curve that the electrode prepared in reference examples 1 is recorded under the same terms, respectively corresponds curve d, e, f in Fig. 4；
The electrode for preparing in record embodiment 1, the electrode prepared in embodiment 1 are in conjunction with 5 × 10-6mol·L-1BSM, reality
The electrode prepared in example 1 is applied in conjunction with 1 × 10-5mol·L-1The differential pulse curve of IMI, respectively correspond curve a, b in Fig. 5,
c；The differential pulse curve that the electrode prepared in reference examples 1 is recorded under the same terms, respectively corresponds curve d, e, f in Fig. 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,
There is a pair of of reversible redox peak of polysulfide violet 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 decrease and occur at -0.94V one it is irreversible also
Parent peak.This illustrate mono signal (| Δ iPolysulfide violet|) detection bensulfuron-methyl and dual signal (| Δ iImidacloprid|+|ΔiPolysulfide violet|) measurement imidacloprid
Strategy it is practical.
As shown in Figure 4, Figure 5, when the electrode prepared in reference examples 1 does not have trace cave, bensulfuron-methyl and pyrrole cannot be combined
Worm quinoline molecule, while also without the electron transfer pathways of polysulfide violet.Therefore, the characteristic peak of polysulfide violet and imidacloprid is all without going 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、1.0×10-5The differential pulse curve of mol/L；Being continuously added to imidacloprid concentration is 1.0 × 10-7mol/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 for preparing in embodiment 1 in the bensulfuron-methyl that various concentration is added
With curent change caused by imidacloprid, calibration curve is drawn, 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-methylDirectly 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 with concentration for 1.0 × 10-5mol·L-1Bensulfuron-methyl solution in polysulfide violet reduction peak current value on the basis of,
The sum of dual signal absolute value that imidacloprid and polysulfide violet are constituted (| Δ iImidacloprid|+|ΔiPolysulfide violet|) and 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 are limited to 6.5 × 10-8Mol/L (S/N=3) (see Fig. 6).
Detect example 3: selectivity
Select the chaff interferent of Garagard (TB), pyrazosulfuron (PSE) as bensulfuron-methyl；Thiacloprid (THI), Acker are safe
(THIM) as the chaff interferent of imidacloprid, the structural formula of bensulfuron-methyl and imidacloprid sees below text, prepares in record record embodiment 1
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 interferents.
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 interferent.
Detect example 4: repeatability, reproducibility and stability
5 electrodes are prepared for using the method for embodiment 1, with differential pulse voltametry detection 5.0 × 10-6mol·L-1Benzyl
Sulfometuron Methyl, obtains five groups of response current values, and relative standard deviation (RSD) is 3.6%；Detection 5.0 × 10-5mol·L-1Imidacloprid
Five groups of response current values are obtained, relative standard deviation (RSD) is 4.5%, shows that the sensor of preparation has repeatability well.
Electrode prepared by the method for same root embodiment 1 is eluted in conjunction with being repeated 5 times, detection 5.0 × 10- 6mol·L-1Bensulfuron-methyl and 5.0 × 10-5mol·L-1Imidacloprid, obtained relative standard deviation (RSD) are respectively 3.8% He
4.7%, show that prepared sensor has good reproducibility.
Prepared modified electrode is placed at 4 DEG C and is saved, every three days with differential pulse voltametry detect 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 two weeks for discovery
The 94.5% of beginning electric current and 92.1%, show that the sensor of preparation has good stability.
Detect example 5: actual sample detection
Rice field water is selected as actual sample to evaluate embodiment 1, embodiment 2, the sensor prepared in embodiment 3 and answer
Use ability.Actual sample processing step is as follows: taking the rice field 2mL water to be put into supercentrifuge centrifugation half under 4000rpm revolving speed small
When, it takes supernatant liquor pH=5.0,0.1molL-1PBS to be diluted to 5mL, is detected using standard addition method.As a result such as
Shown in table 1, for the rate of recovery between 94.6%-104.5%, relative standard deviation shows the electrochemistry in 2.0%-4.8%
Sensor can be used for the detection of bensulfuron-methyl and imidacloprid in actual water sample.
The calculation method of the rate of recovery: the rate of recovery=sensor detection limit/additional amount × 100%
Table 1
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
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 also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of preparation method of double-template trace electrochemical sensor, which comprises 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 modified to bensulfuron-methyl and imidacloprid；
(2) electrode that bensulfuron-methyl and imidacloprid are modified is impregnated in acid solution, elutes bensulfuron-methyl and imidacloprid；
Wherein, in step (1), the ratio between o-phenylenediamine, bensulfuron-methyl, amount of substance of imidacloprid are as follows: 10:1~3:2~4；
Wherein, in step (1), relative to the mixed liquor of 1L, the concentration of o-phenylenediamine is 8~12mmolL-1, bensulfuron-methyl
Concentration be 1~3mmolL-1, the concentration of imidacloprid is 2~4mmolL-1；
Wherein, in step (1), the pH value of mixed liquor is 4~8；
Wherein, the condition of electropolymerization are as follows: polymerization current potential is -0.4V~+0.8V；Polymerization circle number is 10~50 circles；Scanning speed is
45~55mVs-1。
2. preparation method according to claim 1, wherein mixed liquor includes phosphate buffer and acetonitrile.
3. preparation method according to claim 2, wherein the volume ratio of phosphate buffer and acetonitrile be 3:1.5~
2.5。
4. preparation method according to claim 2 or 3, wherein the concentration of phosphate buffer is 0.08~0.12mol
L-1。
5. 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 of liquid is a variety of.
6. preparation method according to claim 1 or 5, wherein soaking time is 10~20min.
7. preparation method according to claim 5, wherein in step (2), in acid solution hydrionic concentration be 0.30~
0.70mol·L-1。
8. preparation method according to claim 7, wherein acid solution is hydrochloric acid.
9. a kind of double-template trace electrochemical sensor, which is characterized in that pass through the described in any item preparation sides claim 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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