CN106198701A - A kind of metal-organic framework material area load molecular imprinted polymer membrane is for the electrochemical detection method of orthene - Google Patents
A kind of metal-organic framework material area load molecular imprinted polymer membrane is for the electrochemical detection method of orthene Download PDFInfo
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- CN106198701A CN106198701A CN201610684006.4A CN201610684006A CN106198701A CN 106198701 A CN106198701 A CN 106198701A CN 201610684006 A CN201610684006 A CN 201610684006A CN 106198701 A CN106198701 A CN 106198701A
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- metal
- imprinted polymer
- framework material
- orthene
- organic framework
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Abstract
The present invention relates to a kind of metal-organic framework material area load molecular imprinted polymer membrane electrochemical detection method for orthene, with copper nitrate and 4, the metal-organic framework material that 4' biphenyl dicarboxylic acid is formed is support, orthene is template molecule, methacrylic acid is function monomer, ethylene glycol dimethacrylate is cross-linking agent, azodiisobutyronitrile is initiator, synthesize metal framework material surface supporting molecular imprinted polymer film, ultrasonic disperse is spin coating electrode surface in nafion solution, use differential pulse voltammetry that orthene is detected.The present invention has obtained the molecularly imprinted polymer that specific surface area is big, mass transfer velocity is fast, and for the detection of orthene, the method has good stability, highly sensitive.
Description
Technical field
The present invention relates to the detection method of pesticide residue orthene, specifically a kind of metal organic frame material
Material area load molecular imprinted polymer membrane preparation detects orthene for electrochemical method.
Background technology
Organophosphorus pesticide is the organic compound that a class is phosphorous.Compared with other kinds of pesticide, organophosphorus pesticide has
The feature that insecticidal spectrum is wide, drug effect is high, residual period is short and cheap, is currently used widest in area, the agriculture that consumption is maximum of China
Medicine.Arthropod and mammal can be caused acetylcholine to accumulate by organophosphorus pesticide, cause delayed ischemic neurological deficits, thus cause
Damage to human body.Owing to part organophosphorus pesticide toxicity is relatively big, it is prohibited from using, has sold, such as Bayer 71628, to sulfur
Phosphorus, parathion-methyl, Azodrin, phosphamidon etc..Owing to orthene generates toxicity higher organophosphor agriculture in degradation process
Medicine Bayer 71628, so orthene the most still remains greater risk, I crosses regulation orthene in vegetable
Big residual quantity is 1mg/kg.
Method is analyzed in Pesticides Testing at present mainly to be had: chromatography, inhibiting AChE, immunological method, chemoluminescence method etc..Color
Spectrometry is the method for the most commonly used detection pesticide, owing in general institute test sample product, impurity is more, is easily subject to interference, generally exists
Need before analysis sample is carried out pre-treatment, improve accuracy and the sensitivity of method.The sensitivity of inhibiting AChE is general
Poor, repetitive rate, the response rate are relatively low, and the sensitivity to different pesticide is different, so applying in general to the quick detection at scene
And the selective mechanisms of gross sample.The selectivity of reagent is required higher by immunological method, needs synthesis in advance relatively during detection
The artificial antigen answered.The most single workload of haptenic synthesis is big, the cycle is long, and pesticide that may be similar with pesticide structure to be measured
Or there is cross reaction in various degree in pesticide metabolism thing to be measured.The selectivity of chemoluminescence method detection is poor, and most
Analysis sample composition is complicated, so being generally combined with isolation technics by chemiluminescence, to reach ideal effect.Therefore, build
Vertical a kind of high sensitivity and the method for specific Rapid Screening pesticide residue, become and need solution badly for this research field current
One of problem.
Metal-organic framework material, is that a class has high porosity, high-specific surface area, the adjustable compound of structure, utilizes
Its character advantage binding molecule blotting membrane material can improve adsorbance.Molecular engram sensitive material and biological sensitive materials are as raw
Thing enzyme, antigen-antibody etc. are compared, and not only have high temperature resistant, high pressure, organic solvent, acid, alkali etc., and can be repeated several times and make
With；Molecularly imprinted polymer material has high selectivity, a high adsorption to target molecule simultaneously, and therefore it compares and is suitable as electricity
The sensitive material of chemical sensor, is assembled into the electrochemical sensor of molecular engram.Additionally, with conventional and traditional sensory device
Material is compared, and it has preferable selectivity, good stability to target compound, is passed as electrochemistry by molecular engram material
The sensing unit of sensor, is then converted into by electrochemical means and can measure the signal of telecommunication, can be used for high selection quantitative analysis acetyl
Bayer 71628 material.
Summary of the invention
It is an object of the invention to set up a kind of metal-organic framework material area load molecular imprinted polymer membrane for
The electrochemical detection method of orthene.
Described a kind of metal-organic framework material area load molecular imprinted polymer membrane is for the electricity of orthene
Chemical detection method process is as follows:
(1) copper nitrate and 4,4'-biphenyl dicarboxylic acid solution is placed in reactor, after hydro-thermal reaction, washs, is dried, and obtaining metal has
Machine frame material C u (BPDA)；
(2) function monomer of orthene molecular imprinted polymer membrane is selected；
(3) with the Cu (BPDA) that obtains in (1) as support, by template molecule, function monomer, cross-linking agent, porogen and initiation
Agent mix homogeneously, prepares metal-organic framework material area load imprinted polymer solution；
(4) utilize apparatus,Soxhlet's to get rid of template molecule in its molecularly imprinted polymer by eluant, obtain Cu (BPDA)
MIP；
(5) take in a certain amount of (4) and obtain Cu (BPDA)@MIP in nafion solution, ultrasonic disperse, it is spun on electrode surface；
(6) electrode be placed in the buffer solution containing orthene absorption certain time, redistilled water wash, be placed in containing
The blank buffer solution of thionine uses differential pulse voltammetry detection.
Described a kind of metal-organic framework material area load molecular imprinted polymer membrane is for the electricity of orthene
Chemical detection method specifically comprises the following steps that
(1) preparation of metal-organic framework material Cu (BPDA): take 1.2 g copper nitrates, 1 g 4,4'-biphenyl dicarboxylic acid, dissolve
In 10 mL redistilled waters, 10 mL N,N-dimethylformamides and 10 mL methyl alcohol mixed liquors；Fully mixing is placed in 50 mL
In inner liner polytetrafluoroethylene reactor inner bag, react 24 h at 130 DEG C, successively with DMF and second distillation
Water washs 3 times, and 70 DEG C are dried 2 h, obtain Cu (BPDA) material.
(2) function monomer of the orthene molecular imprinted polymer membrane described in invention is methacrylic acid.
(3) cross-linking agent of the present invention is ethylene glycol dimethacrylate, porogen be acetonitrile, initiator be azo
Bis-isobutyronitrile.
(4) add 0.05 g metal-organic framework material Cu (BPDA), 10 mL acetonitriles, add 0.386 g orthene
It is sufficiently stirred for making it be completely dissolved, is subsequently adding 0.68 mL methacrylic acid, is sufficiently stirred for 1h, add the second two of 0.60 mL
Alcohol dimethylacrylate and 40 mg azodiisobutyronitriles, then 60 DEG C of water-baths are polymerized 24 h, obtain Cu (BPDA)@MIP.
(5) take above-mentioned substance Cu (BPDA)@MIP and be placed in apparatus,Soxhlet's, add 135 mL methanol and 15 mL glacial acetic acids do
Eluant, continuous eluting 48 h, without orthene to eluent, 70 DEG C of vacuum drying, obtain dry metal framework material
The molecular imprinted polymer membrane supported.
(6) take 0.02g Cu (BPDA)@MIP and insert 1mL 5% nafion solution, ultrasonic disperse, spin coating glass-carbon electrode table
Face.
(7) (6) are prepared electrode to be placed in the phosphate buffer solution of pH 6.2 of the orthene containing variable concentrations
Adsorbing 10 min, redistilled water washs 3 times, and the phosphoric acid blank that electrode is placed in the pH6.2 containing 0.1mmol/L thionine is delayed
Dissolved liquid, uses differential pulse voltammetry detection, scanning voltage 0-0.6V.
Beneficial effects of the present invention:
(1) present invention uses metal framework material to synthesize, as support, the molecular engram that specific surface area is big, mass transfer velocity is fast
Polymeric film.
(2) orthene molecularly imprinted polymer selectivity of the present invention is strong, has orthene special
Property identification.
(3) present invention is with low cost, experimental implementation is simple, easy control of reaction conditions.
(4) present invention is for the detection of orthene, has good stability, highly sensitive.
Detailed description of the invention
Below the specific embodiment of the present invention is illustrated: a kind of metal-organic framework material area load molecular engram
Polymeric film is for the electrochemical detection method of orthene.
Embodiment 1: orthene detection in environmental water sample
(1) preparation of metal-organic framework material Cu (BPDA): take 1.2 g copper nitrates, 1g 4,4'-biphenyl dicarboxylic acid, dissolve
In 10 mL redistilled waters, 10 mL N,N-dimethylformamides and 10 mL methyl alcohol mixed liquors；Fully mixing is placed in 50 mL
In inner liner polytetrafluoroethylene reactor inner bag, react 24 h at 130 DEG C, obtain stick solid, successively with N, N-dimethyl formyl
Amine and redistilled water wash 3 times, and 70 DEG C are dried 2 h, obtain metal-organic framework material Cu (BPDA).
(2) with metal-organic framework material as support, using methacrylic acid is that function monomer prepares orthene
Molecular imprinted polymer membrane.First addition 0.05g metal-organic framework material Cu (BPDA) in 100 mL round-bottomed flasks, 10
ML acetonitrile, adds 0.386 g orthene and is sufficiently stirred for making it be completely dissolved；It is subsequently adding 0.68 mL methacrylic acid,
It is sufficiently stirred for 1 h, adds ethylene glycol dimethacrylate and the 40 mg azodiisobutyronitriles of 0.60 mL subsequently, then 60
It is polymerized 24 h under DEG C water-bath magnetic agitation, obtains metal-organic framework material area load molecular imprinted polymer membrane Cu (BPDA)@
MIP。
(3) take above-mentioned substance Cu (BPDA)@MIP and be placed in apparatus,Soxhlet's, add 135 mL methanol and 15 mL glacial acetic acids do
Eluant, continuous eluting 48 h, to eluent without orthene, 70 DEG C of vacuum drying, obtain being dried metal framework material and prop up
The molecular imprinted polymer membrane held.
(4) taking 0.02 g Cu (BPDA)@MIP and add 1 mL 5% nafion solution, ultrasonic disperse is uniform, uses spin coating
Machine is uniformly spun on glassy carbon electrode surface.
(5) preparation is prepared the 0.01 mol/L phosphoric acid that electrode is placed in the pH 6.2 of the orthene containing variable concentrations
Buffer solution adsorbs 10 min, takes out electrode redistilled water and wash 3 times, electrode is placed in containing 0.1 mmol/L thionine
The 0.01 mol/L phosphoric acid blank buffer solution of pH 6.2, uses differential pulse voltammetry detection, scanning voltage 0-0.6 V；Paint
Working curve processed.
(6) actual water sample processes: gathers river, lake water actual sample, by the membrane filtration that aperture is 0.22 μm, takes
Filtrate 5.0 mL, adds 5.0 mL pH 6.2 0.01 mol/L phosphate buffer solutions, is placed in sample by modification working electrode
10 min, after taking-up electrode redistilled water cleans 3 times, electrode is placed in 0.01 of the pH 6.2 containing 0.1mmol/L thionine
Mol/L phosphoric acid blank buffer solution, uses differential pulse voltammetry detection.Therefore, bear based on metal-organic framework material surface
Carrying molecular imprinted polymer membrane to be used for detecting orthene, the method achieve easy and simple to handle, quickly, expense is low and without specially
Industry personage can detect orthene.
Claims (8)
1. a metal-organic framework material area load molecular imprinted polymer membrane is for the Electrochemical Detection of orthene
Method, is characterized in that comprising the following steps:
(1) copper nitrate and 4,4'-biphenyl dicarboxylic acid solution is placed in reactor, after hydro-thermal reaction, washs, is dried, and obtaining metal has
Machine frame material C u (BPDA)；
(2) function monomer of orthene molecular imprinted polymer membrane is selected；
(3) with the Cu (BPDA) that obtains in (1) as support, by template molecule, function monomer, cross-linking agent, porogen and initiation
Agent mix homogeneously, prepares metal-organic framework material area load imprinted polymer solution；
(4) utilize apparatus,Soxhlet's to get rid of template molecule in its molecularly imprinted polymer by eluant, obtain Cu (BPDA)
MIP；
(5) take in a certain amount of (4) and obtain Cu (BPDA)@MIP in nafion solution, ultrasonic disperse, it is spun on electrode surface；
(6) electrode is placed in the buffer solution containing orthene absorption certain time, after redistilled water washing, is placed in and contains
The blank buffer solution having thionine uses differential pulse voltammetry detection.
A kind of metal-organic framework material area load molecular imprinted polymer membrane the most according to claim 1 is for acetyl
The electrochemical detection method of Bayer 71628, it is characterised in that: in step (1), described metal-organic framework material Cu (BPDA)
Preparation: take 1.2 g copper nitrates, 1g 4,4'-biphenyl dicarboxylic acid, be dissolved in 10 mL redistilled waters, 10 mL N, N-dimethyl
In Methanamide and 10 mL methyl alcohol mixed liquors；Fully mixing is placed in 50 mL inner liner polytetrafluoroethylene reactor inner bags, 130 DEG C
Lower reaction 24 h, washs 3 times with DMF and redistilled water successively, and 70 DEG C are dried 2 h, obtain Cu
(BPDA) material.
A kind of metal-organic framework material area load molecular imprinted polymer membrane the most according to claim 1 is for acetyl
The electrochemical detection method of Bayer 71628, it is characterised in that: in step (2), described orthene molecular imprinted polymer membrane
Function monomer be methacrylic acid.
A kind of metal-organic framework material area load molecular imprinted polymer membrane the most according to claim 1 is for acetyl
The electrochemical detection method of Bayer 71628, it is characterised in that: in step (3), described cross-linking agent is ethyleneglycol dimethacrylate
Ester, porogen be acetonitrile, initiator be azodiisobutyronitrile.
A kind of metal-organic framework material area load molecular imprinted polymer membrane the most according to claim 1 is for acetyl
The electrochemical detection method of Bayer 71628, it is characterised in that: in step (3), described prepares molecularly imprinted polymer: add
0.05g metal-organic framework material Cu (BPDA), 10 mL acetonitriles, add 0.386 g orthene and be sufficiently stirred for making it complete
Dissolve, be subsequently adding 0.68 mL methacrylic acid, be sufficiently stirred for 1h, add the ethylene glycol dimethacrylate of 0.60 mL
With 40 mg azodiisobutyronitriles, then 60 DEG C of water-baths are polymerized 24 h, obtain Cu (BPDA)@MIP.
A kind of metal-organic framework material area load molecular imprinted polymer membrane the most according to claim 1 is for acetyl
The electrochemical detection method of Bayer 71628, it is characterised in that: in step (4), described Cu (BPDA) the@MIP that takes is placed in surname extraction
Device, adds 135 mL methanol and 15 mL glacial acetic acids do eluant, continuous eluting 48 h, to eluent without orthene, and 70
DEG C vacuum drying, obtains the molecular imprinted polymer membrane that dry metal framework material is supported.
A kind of metal-organic framework material area load molecular imprinted polymer membrane the most according to claim 1 is for acetyl
The electrochemical detection method of Bayer 71628, it is characterised in that: in step (5), described in take 0.02 g and be dried Cu (BPDA)@MIP and put
Enter 1mL 5% nafion solution, ultrasonic disperse, spin coating glassy carbon electrode surface.
A kind of metal-organic framework material area load molecular imprinted polymer membrane the most according to claim 1 is for acetyl
The electrochemical detection method of Bayer 71628, it is characterised in that: in step (6), described electrode is placed in the acetyl first containing variable concentrations
The phosphate buffer solution of the pH 6.2 of amine phosphorus adsorbs 10 min, redistilled water washing electrode 3 times, electrode is placed in containing
The phosphoric acid blank buffer solution of the pH 6.2 of 0.1 mmol/L thionine, uses differential pulse voltammetry detection, scanning voltage 0-
0.6 V。
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| CN106501335A (en) * | 2017-01-09 | 2017-03-15 | 广西民族大学 | A kind of preparation method of highly sensitive estazolam molecular imprinting electrochemical sensor |
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| CN106546651A (en) * | 2017-01-09 | 2017-03-29 | 广西民族大学 | A kind of preparation method of highly sensitive isocarboxazid molecular imprinting electrochemical sensor |
| CN106596680A (en) * | 2017-01-09 | 2017-04-26 | 广西民族大学 | Preparation method of high-sensitivity mirtazapine molecularly-imprinted electrochemical sensor |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040126814A1 (en) * | 2000-08-21 | 2004-07-01 | Singh Waheguru Pal | Sensor having molecularly imprinted polymers |
| CN101666774A (en) * | 2009-09-29 | 2010-03-10 | 济南大学 | Method for preparing glycosyl functional molecularly imprinted membrane electrode for detecting bacterial toxin and application thereof |
| CN102898566A (en) * | 2011-07-28 | 2013-01-30 | 天津科技大学 | Preparation method of metal organic framework molecularly imprinted polymer used for enriching trace amounts of Metolcarb |
| CN104014320A (en) * | 2014-06-19 | 2014-09-03 | 天津科技大学 | Aqueous phase metal organic framework molecular imprinting material of enriched trace meta-tolyl-N-methylcarbamate (MTMC) |
| CN105203606A (en) * | 2015-10-27 | 2015-12-30 | 南开大学 | Preparation method and application of copper metal organic framework complex-based modified gold electrode |
-
2016
- 2016-08-18 CN CN201610684006.4A patent/CN106198701B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040126814A1 (en) * | 2000-08-21 | 2004-07-01 | Singh Waheguru Pal | Sensor having molecularly imprinted polymers |
| CN101666774A (en) * | 2009-09-29 | 2010-03-10 | 济南大学 | Method for preparing glycosyl functional molecularly imprinted membrane electrode for detecting bacterial toxin and application thereof |
| CN102898566A (en) * | 2011-07-28 | 2013-01-30 | 天津科技大学 | Preparation method of metal organic framework molecularly imprinted polymer used for enriching trace amounts of Metolcarb |
| CN104014320A (en) * | 2014-06-19 | 2014-09-03 | 天津科技大学 | Aqueous phase metal organic framework molecular imprinting material of enriched trace meta-tolyl-N-methylcarbamate (MTMC) |
| CN105203606A (en) * | 2015-10-27 | 2015-12-30 | 南开大学 | Preparation method and application of copper metal organic framework complex-based modified gold electrode |
Non-Patent Citations (3)
| Title |
|---|
| KUN QIAN ET AL.: "Metal–organic frameworks supported surface–imprinted nanoparticles for the sensitive detection of metolcarb", 《BIOSENSORS AND BIOELECTRONICS》 * |
| S. E. MOUSAVINIA ET AL.: "Novel nanorose-like Ce(III)-doped and undoped Cu(II)–biphenyl-4,4-dicarboxylic acid (Cu(II)–BPDCA) MOSs as visible light photocatalysts: synthesis, characterization, photodegradation of toxic dyes and optimization", 《PHYS.CHEM.CHEM.PHYS.》 * |
| YUQING DUAN ET AL.: "A computational approach to design an electrochemical sensor and determination of acephate in aqueous solution based on a molecularly imprinted poly(o-phenylenediamine) film", 《ANALYTICAL METHODS》 * |
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