CN106198701B - A kind of metal-organic framework material area load molecular imprinted polymer membrane is used for the electrochemical detection method of orthene - Google Patents
A kind of metal-organic framework material area load molecular imprinted polymer membrane is used for the electrochemical detection method of orthene Download PDFInfo
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- CN106198701B CN106198701B CN201610684006.4A CN201610684006A CN106198701B CN 106198701 B CN106198701 B CN 106198701B CN 201610684006 A CN201610684006 A CN 201610684006A CN 106198701 B CN106198701 B CN 106198701B
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Abstract
The present invention relates to the electrochemical detection methods that a kind of metal-organic framework material area load molecular imprinted polymer membrane is used 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 crosslinking agent, azodiisobutyronitrile is initiator, metal framework material surface supporting molecular imprinted polymer film is synthesized, ultrasonic disperse spin coating electrode surface in nafion solution, orthene is detected using differential pulse voltammetry.The present invention has obtained the fast molecularly imprinted polymer of large specific surface area, mass transfer velocity, and for the detection of orthene, this method has stability good, high sensitivity.
Description
Technical field
The present invention relates to the detection method of pesticide residue orthene, specifically a kind of metal organic frame material
Expect that the preparation of area load molecular imprinted polymer membrane detects orthene for electrochemical method.
Background technique
Organophosphorus pesticide is a kind of phosphorous organic compound.Compared with other kinds of pesticide, organophosphorus pesticide has
Insecticidal spectrum is wide, drug effect is high, residual life is short and cheap feature, is that the current use scope in China is most wide, the maximum agriculture of dosage
Medicine.Organophosphorus pesticide will cause acetylcholine accumulation to arthropod and mammal, cause neurological dysfunction, so as to cause
Damage to human body.It since part organophosphorus pesticide is more toxic, has been prohibited from using, has sold at present, such as acephatemet, to sulphur
Phosphorus, parathion-methyl, Azodrin, phosphamidon etc..Since orthene generates the higher organic phosphorus agriculture of toxicity in degradation process
Medicine acephatemet, so orthene still remains greater risk in the environment, I crosses regulation orthene in vegetables most
Big residual quantity is 1mg/kg.
Pesticides Testing analysis method mainly has at present: chromatography, enzyme inhibition, immunological method, chemoluminescence method etc..Color
Spectrometry is that the method for the most commonly used detection pesticide is easy to be interfered, usually exist since impurity is more in general institute's sample
It needs to carry out pre-treatment to sample before analysis, comes the accuracy and sensitivity of improvement method.The sensitivity of enzyme inhibition is general
Poor, repetitive rate, the rate of recovery are lower, and to the sensitivity of different pesticides difference, so applying in general to the quick detection at scene
And the selective mechanisms of gross sample.Immunological method is more demanding to the selectivity of reagent, needs when detection synthesis in advance opposite
The artificial antigen answered.The not single heavy workload of the synthesis of haptens, period are long, and pesticide that may be similar with pesticide structure to be measured
Or different degrees of cross reaction occurs for pesticide metabolism object to be measured.The selectivity of chemoluminescence method detection is poor, and most of
It is complicated to analyze sample composition, so being usually combined chemiluminescence and isolation technics, to reach ideal effect.Therefore, it builds
The method for founding a kind of highly sensitive and specificity Rapid Screening pesticide residue becomes as the current research field urgent need to resolve
One of the problem of.
Metal-organic framework material is a kind of with high porosity, high-specific surface area, the adjustable compound of structure, is utilized
Adsorbance can be improved in its property advantage binding molecule trace membrane material.Molecular engram sensitive material and biological sensitive materials are such as raw
Object 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 made
With；Molecularly imprinted polymer material has highly selective, high adsorption to target molecule simultaneously, therefore it is relatively suitable as electricity
The sensitive material of chemical sensor is assembled into the electrochemical sensor of molecular engram.In addition, with conventional and traditional sensory device
Material is compared, it has preferable selectivity, good stability to target compound, is passed molecular engram material as electrochemistry
Then the sensing unit of sensor is converted into can measure electric signal by electrochemical means, can be used for high selection quantitative analysis acetyl
Methylamine phosphorus substance.
Summary of the invention
It is an object of the invention to establish a kind of metal-organic framework material area load molecular imprinted polymer membrane to be used for
The electrochemical detection method of orthene.
A kind of metal-organic framework material area load molecular imprinted polymer membrane is used for the electricity of orthene
Chemical detection method process is as follows:
(1) copper nitrate and 4,4'- biphenyl dicarboxylic acid solution are placed in reaction kettle, washing, dry after hydro-thermal reaction, obtain gold
Belong to organic framework materials Cu (BPDA)；
(2) function monomer of orthene molecular imprinted polymer membrane is selected；
(3) with Cu obtained in (1) (BPDA) be support, by template molecule, function monomer, crosslinking agent, pore-foaming agent and
Initiator is uniformly mixed, and prepares the molecularly imprinted polymer of the non-eluted template of metal-organic framework material area load；
(4) point of the non-eluted template of metal-organic framework material area load is got rid of using Soxhlet extractor and eluant, eluent
Template molecule in sub- imprinted polymer obtains metal-organic framework material area load molecular imprinted polymer membrane Cu (BPDA)@
MIP；
(5) it takes and obtains Cu (BPDA)@MIP in a certain amount of (4) in nafion solution, ultrasonic disperse is spun on electrode table
Face；
(6) electrode, which is placed in the buffer solution containing orthene, adsorbs certain time, and second distillation water washing is placed in
Blank buffer solution containing thionine is detected using differential pulse voltammetry.
A kind of metal-organic framework material area load molecular imprinted polymer membrane is used for the electricity of orthene
Specific step is as follows for chemical detection method:
(1) preparation of metal-organic framework material Cu (BPDA): taking 1.2 g copper nitrates, 1 g 4,4'- biphenyl dicarboxylic acid,
It is dissolved in 10 mL secondary distilled waters, 10 mL N,N-dimethylformamides and 10 mL methyl alcohol mixed liquors；It mixes well and is placed in
In 50 mL inner liner polytetrafluoroethylene reaction kettle liners, 24 h are reacted at 130 DEG C, successively with n,N-Dimethylformamide and secondary
Distillation water washing 3 times, 70 DEG C of 2 h of drying obtain Cu (BPDA) material.
(2) function monomer of the invention orthene molecular imprinted polymer membrane is methacrylic acid.
(3) crosslinking agent of the present invention is ethylene glycol dimethacrylate, and pore-foaming agent is acetonitrile, initiator is azo
Bis-isobutyronitrile.
(4) 0.05 g metal-organic framework material Cu (BPDA) is added, 0.386 g orthene is added in 10 mL acetonitriles
It is sufficiently stirred and makes it completely dissolved, 0.68 mL methacrylic acid is then added, 1h is sufficiently stirred, the second two of 0.60 mL is added
Alcohol dimethylacrylate and 40 mg azodiisobutyronitriles, then 60 DEG C of water-baths polymerize 24 h, obtain metal-organic framework material
The molecular imprinted polymer membrane of the non-eluted template of area load.
(5) molecular engram for the non-eluted template of metal-organic framework material area load for taking above-mentioned steps (4) to obtain is poly-
Compound film substance is placed in Soxhlet extractor, and 135 mL methanol are added and 15 mL glacial acetic acids make eluant, eluent, continuous to elute 48 h, until
Without orthene in eluent, 70 DEG C of vacuum drying obtain the molecular imprinted polymer membrane that dry metal framework material is supported
Cu(BPDA)@MIP。
(6) 0.02g Cu (BPDA)@MIP is taken to be placed in 5% nafion solution of 1mL, ultrasonic disperse, spin coating glass-carbon electrode table
Face.
(7) electrode is made in (6) to be placed in the phosphate buffer solution of pH 6.2 of the orthene containing various concentration
10 min are adsorbed, second distillation water washing 3 times, the phosphoric acid blank that electrode is placed in the pH6.2 containing 0.1mmol/L thionine are delayed
Solution is rushed, is detected using differential pulse voltammetry, scanning voltage 0-0.6V.
Beneficial effects of the present invention:
(1) present invention synthesizes the fast molecule of large specific surface area, mass transfer velocity as support using metal framework material
Imprinted polymer film.
(2) orthene molecularly imprinted polymer of the present invention is selectively strong, has to orthene special
Property identification.
(3) present invention is low in cost, experimental implementation is simple, easy control of reaction conditions.
(4) present invention is used for the detection of orthene, has stability good, high sensitivity.
Specific embodiment
Specific embodiment of the invention is illustrated below: a kind of metal-organic framework material area load molecular engram
Polymer film is used for the electrochemical detection method of orthene.
Embodiment 1: for orthene detection in environmental water sample
(1) preparation of metal-organic framework material Cu (BPDA): taking 1.2 g copper nitrates, 1g 4,4'- biphenyl dicarboxylic acid,
It is dissolved in 10 mL secondary distilled waters, 10 mL N,N-dimethylformamides and 10 mL methyl alcohol mixed liquors；It mixes well and is placed in
In 50 mL inner liner polytetrafluoroethylene reaction kettle liners, 24 h are reacted at 130 DEG C, obtain stick solid, successively use N, N- diformazan
Base formamide and second distillation water washing 3 times, 70 DEG C of 2 h of drying obtain metal-organic framework material Cu (BPDA).
(2) using metal-organic framework material as support, methacrylic acid is used to prepare orthene for function monomer
Molecular imprinted polymer membrane.0.05g metal-organic framework material Cu (BPDA) is added first in 100 mL round-bottomed flasks, 10
ML acetonitrile, 0.386 g orthene of addition, which is sufficiently stirred, to be made it completely dissolved；Then 0.68 mL methacrylic acid is added,
1 h is sufficiently stirred, then adds the ethylene glycol dimethacrylate and 40 mg azodiisobutyronitriles of 0.60 mL, then 60
It polymerize 24 h under DEG C water-bath magnetic agitation, obtains the non-eluted template molecularly imprinted polymer of metal-organic framework material area load
Film.
(3) it takes substance obtained in above-mentioned steps (2) to be placed in Soxhlet extractor, 135 mL methanol and 15 mL ice second is added
Acid makees eluant, eluent, continuous to elute 48 h, until eluent, without orthene, 70 DEG C of vacuum drying obtain metal organic frame material
Expect area load molecular imprinted polymer membrane Cu (BPDA)@MIP.
(4) 0.02 g Cu (BPDA)@MIP is taken to be placed in 1 mL, 5% nafion solution, ultrasonic disperse is uniform, and use is even
Glue machine is uniformly spun on glassy carbon electrode surface.
(5) the 0.01 mol/L phosphoric acid that the pH 6.2 that electrode is placed in the orthene containing various concentration is made will be prepared
10 min are adsorbed in buffer solution, take out electrode second distillation water washing 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, is detected, scanning voltage 0-0.6 V using differential pulse voltammetry；It draws
Working curve processed.
(6) actual water sample is handled: acquisition river water, lake water actual sample, the membrane filtration for being 0.22 μm by aperture take
5.0 mL pH, 6.2 0.01 mol/L phosphate buffer solution is added in 5.0 mL of filtrate, and modification working electrode is placed in sample
10 min, after taking out the cleaning of electrode secondary distilled water 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, is detected using differential pulse voltammetry.Therefore, negative based on metal-organic framework material surface
Molecular imprinted polymer membrane is carried for detecting orthene, the method achieve easy to operate, quickly, expense is low and without special
Industry personage can be detected orthene.
Claims (6)
1. the Electrochemical Detection that a kind of metal-organic framework material area load molecular imprinted polymer membrane is used for orthene
Method, it is characterized in that the following steps are included:
It (1) is methyl by orthene template molecule, function monomer with metal-organic framework material Cu (BPDA) for support
Acrylic acid, crosslinking agent are ethylene glycol dimethacrylate, pore-foaming agent is acetonitrile and initiator is that azodiisobutyronitrile mixing is equal
It is even, prepare the molecular imprinted polymer membrane of the non-eluted template of metal-organic framework material area load；
(2) the metal-organic framework material area load that (1) obtains is got rid of using Soxhlet extractor and eluant, eluent do not elute mould
Orthene template molecule in the molecular imprinted polymer membrane of plate obtains metal-organic framework material area load molecular engram
Polymer film Cu (BPDA)@MIP；
(3) taking Cu (BPDA)@MIP obtained in a certain amount of (2), in nafion solution, ultrasonic disperse is spun on electrode surface；
(4) electrode of step (3) preparation, which is placed in the buffer solution containing orthene, adsorbs certain time, secondary distilled water
After washing, it is placed in the blank buffer solution containing thionine and is detected using differential pulse voltammetry.
2. a kind of metal-organic framework material area load molecular imprinted polymer membrane according to claim 1 is used for acetyl
The electrochemical detection method of acephatemet, it is characterised in that: in step (1), the metal-organic framework material Cu's (BPDA)
Preparation: 1.2 g copper nitrates, 1g 4 are taken, 4'- biphenyl dicarboxylic acid is dissolved in 10 mL secondary distilled waters, 10 mL N, N- dimethyl
In formamide and 10 mL methyl alcohol mixed liquors；It mixes well and is placed in 50 mL inner liner polytetrafluoroethylene reaction kettle liners, 130 DEG C
24 h of lower reaction, successively use n,N-Dimethylformamide and second distillation water washing 3 times, and 70 DEG C of 2 h of drying obtain Cu
(BPDA) material.
3. a kind of metal-organic framework material area load molecular imprinted polymer membrane according to claim 1 is used for acetyl
The electrochemical detection method of acephatemet, it is characterised in that: in step (1), the metal-organic framework material area load is not
The preparation of the molecular imprinted polymer membrane of eluted template: being added 0.05g metal-organic framework material Cu (BPDA), 10 mL acetonitriles,
It 0.386 g orthene is added is sufficiently stirred and make it completely dissolved, 0.68 mL methacrylic acid is then added, is sufficiently stirred
The ethylene glycol dimethacrylate and 40 mg azodiisobutyronitriles of 0.60 mL is added in 1h, then 60 DEG C of water-bath polymerizations 24
H obtains the molecular imprinted polymer membrane of the non-eluted template of metal-organic framework material area load.
4. a kind of metal-organic framework material area load molecular imprinted polymer membrane according to claim 1 is used for acetyl
The electrochemical detection method of acephatemet, it is characterised in that: in step (2), the metal-organic framework material area load is not
The molecularly imprinted polymer of eluted template is placed in Soxhlet extractor, and 135 mL methanol are added and 15 mL glacial acetic acids make eluant, eluent, even
48 h of continuous elution, until eluent, without orthene, 70 DEG C of vacuum drying obtain dry Cu (BPDA)@MIP.
5. a kind of metal-organic framework material area load molecular imprinted polymer membrane according to claim 1 is used for acetyl
The electrochemical detection method of acephatemet, it is characterised in that: in step (3), Cu (BPDA) the@MIP of 0.02 g is taken to be placed in 1mL
In 5% nafion solution, ultrasonic disperse, spin coating glassy carbon electrode surface.
6. a kind of metal-organic framework material area load molecular imprinted polymer membrane according to claim 1 is used for acetyl
The electrochemical detection method of acephatemet, it is characterised in that: in step (4), the electrode is placed in the acetyl first containing various concentration
Adsorb 10 min in the phosphate buffer solution of the pH 6.2 of amine phosphorus, second distillation water washing electrode 3 times, by electrode be placed in containing
The phosphoric acid blank buffer solution of the pH 6.2 of 0.1 mmol/L thionine, is detected, scanning voltage 0- using differential pulse voltammetry
0.6 V。
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| US20040126814A1 (en) * | 2000-08-21 | 2004-07-01 | Singh Waheguru Pal | Sensor having molecularly imprinted polymers |
| CN101666774B (en) * | 2009-09-29 | 2012-10-31 | 济南大学 | Method for preparing glycosyl functional molecularly imprinted membrane electrode for detecting bacterial toxin and application thereof |
| CN102898566B (en) * | 2011-07-28 | 2015-04-01 | 天津科技大学 | Preparation method of metal organic framework molecularly imprinted polymer used for enriching trace amounts of Metolcarb |
| CN104014320B (en) * | 2014-06-19 | 2016-08-17 | 天津科技大学 | A kind of aqueous metal organic frame molecular engram material of enriched with trace meta-tolyl-N-methylcarbamate (MTMC) |
| CN105203606B (en) * | 2015-10-27 | 2018-12-18 | 南开大学 | A kind of preparation method and applications based on copper metal organic frame complex modified gold electrode |
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