CN102863586A - Method for preparing parathion molecular imprinting polymer for water quality detection - Google Patents
Method for preparing parathion molecular imprinting polymer for water quality detection Download PDFInfo
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- CN102863586A CN102863586A CN2012103689197A CN201210368919A CN102863586A CN 102863586 A CN102863586 A CN 102863586A CN 2012103689197 A CN2012103689197 A CN 2012103689197A CN 201210368919 A CN201210368919 A CN 201210368919A CN 102863586 A CN102863586 A CN 102863586A
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- imprinted polymer
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Abstract
The invention discloses a method for preparing a parathion molecular imprinting polymer for water quality detection. According to the method, parathion is used as a template molecule to polymerize the parathion molecularly imprinted polymer for organic phosphorus detection in a water environment under the initiation action of ultraviolet light. The parathion molecularly imprinted polymer prepared by the method has the advantages of short polymerization time and favorable adsorbability; and when the prepared parathion molecularly imprinted polymer is used as a solid phase extraction column filler, solid phase extraction-gas phase chromatography can be utilized to quickly and effectively analyze organic phosphorus pesticide in water, and the parathion molecularly imprinted polymer has the advantages of favorable separating effect, less impurity interference, low detection limit, high sensitivity, high precision and favorable recovery effect, and can satisfy the requirements for detecting trace amounts of organic phosphorus in water.
Description
Technical field
The present invention relates to a kind of preparation method of thiophos molecularly imprinted polymer, a kind of light initiating polymerizing reaction prepares the method that the thiophos molecularly imprinted polymer is used in water quality detection specifically.
Background technology
Organophosphorus is to use at present widely one of agricultural chemicals, organophosphorus belongs to nerve poison, can cause people and animals in various degree poisoning and cause environmental pollution, the diseases such as the water that long-term drinking contains organophosphorus can cause human body cancer, arteriosclerosis, cardiovascular diseases, fetal anomaly, stillborn foetus, early dies young, early ageing.Therefore, set up the method for organophosphorus residue amount in the more effective detection water significant.At present, the relevant detection method report that adopts organic phosphorous molecule imprinted polymer to detect the organophosphorus in fruits and vegetables, the soil is more, but few about the detection method report that adopts molecular imprinting identification organophosphorus in the water surrounding.Chinese patent literature CN102535157 discloses a kind of functionalized poly aniline nano material, be included in olefinic function monomer or the olefinic function monomer layer of combination on the surface of this nano material, induce trace polymerization selectivity to occur by the ethylene linkage in the olefinic function monomer layer that is modified at the polyaniline nano fiber surface, the polyaniline of formation nucleocapsid structure-molecularly imprinted polymer mixture.This patent documentation uses nitrobenzene compounds or sterilant as the masterplate molecule, especially adopt 1,3-dinitrobenzene (DNB) or thiophos be as template molecule, obtains the polyaniline-molecularly imprinted polymer mixture for detection of nitrobenzene compounds or sterilant.But it is to carry out polyreaction under azo-initiator causes, and its polymerization time is longer.The people such as Liu Zhen are in " agricultural chemicals thiophos molecularly imprinted polymer synthesizes and the affinity evaluation " literary composition, with thiophos as the masterplate molecule, adopt the synthetic thiophos molecularly imprinted polymer of thermal initiation precipitation polymerization method take Diisopropyl azodicarboxylate as initiator, yet its polymerization time reaches 24h.
Summary of the invention
It is short that the technical issues that need to address of the present invention provide a kind of polymerization reaction time, the preparation method of the thiophos molecularly imprinted polymer that absorption property is good.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of method for preparing water quality detection usefulness thiophos molecularly imprinted polymer, the method is take thiophos as template molecule, the molecularly imprinted polymer that is fit to detect in the water surrounding organophosphorus by the uv-light polymerization preparation, concrete preparation process is as follows:
1) in reactor, adds successively thiophos, monomer and dichloromethane solvent, at 25 ℃ of lower vibration 1h; Then in 4 ℃ environment, place 12h; Described reactor is the chemical fields such as triangular flask, there-necked flask, four-hole boiling flask, reactor reactors commonly used;
2) add linking agent Viscoat 295 and light trigger in the above-mentioned reaction system, mix, then inflated with nitrogen 2min in the reactor vacuumizes sealing again;
3) above-mentioned reactor is placed ice-water bath and regulate UV-light and the distance of ice-water bath underwater reactor, make it carry out photopolymerization reaction, the reaction times is 0.5～2.5h; Described UV-light is the ultraviolet sources such as ultraviolet lamp tube;
4) pulverizing, grind after the block product of gained is taken out, is that methyl alcohol/acetic acid of 9/1 is molten with volume ratio
Agent is carried out extracting to product, and vacuum-drying obtains the thiophos molecularly imprinted polymer.
Further improvement of the present invention is: the parts by weight of each material are in the described reaction system: 1 part of thiophos, monomer 0.5-3 part, 260 parts of methylene dichloride, Viscoat 295 10-50 part, light trigger 1-4 part.
Further improvement of the present invention is: described light trigger is that mass ratio is the benzophenone of 1:1 and the mixture of 2-hydroxy-2-methyl-1-phenyl-1-acetone.
Further improvement of the present invention is: described monomer is any one of 4-vinylpridine (4-VP), methyl methacrylate (MMA), methacrylic acid (MAA) or acrylamide (MA).
Further improvement of the present invention is: described UV-light is 3～11cm from the distance of reactor.
Because the technical progress of having adopted technique scheme, the present invention to obtain is:
The method for preparing the thiophos molecularly imprinted polymer of the present invention is by uv-light polymerization, can shorten polymerization reaction time, and the thiophos binding performance of molecular imprinted polymers that makes is good, can satisfy the testing requirement of underwater trace organophosphorus.
The present invention is take thiophos as template molecule, and the thiophos molecularly imprinted polymer that the function monomer with suitable function base relies on the covalently or non-covalently effect between functional group to form is monomer-template molecule mixture, this monomer-template molecule mixture has the specific recognition effect, can effectively identify organophosphorus.
With the thiophos molecularly imprinted polymer of method preparation of the present invention, affinity and selectivity are high, and the anti-adverse environment ability is strong, good stability, long service life.
Adopt molecular engram solid phase extraction-vapor-phase chromatography can fast and effeciently divide organophosphorus in the agricultural chemicals that SD-1750 in the bleed, Rogor, parathion-methyl, Malathion, thiophos, Chlorpyrifos 94 etc. contain organophosphorus take the polymkeric substance of the present invention preparation as filler, its good separating effect, and impurity disturbs few, detection limit is low, sensitivity, precision are high, recovering effect is good, can satisfy underwater trace organophosphorus testing requirement.
Description of drawings
Fig. 1 is that the thiophos molecularly imprinted polymer that the present invention prepares is used for the reference colour spectrogram that the organophosphorous pesticides method detects the organophosphorus pesticide gained;
Fig. 2 adopts the solvent extraction vapor-phase chromatography to detect the gas chromatogram of organophosphorus pesticide gained.
Embodiment
Below in conjunction with embodiment the present invention is described in further details:
Various material used in the present invention is as follows: thiophos is standard substance 100 μ gmL
1, State center for standard matter; 4-vinylpridine (4-VP) analytical pure, Acros company; Acrylamide (MA) Sigma company, analytical pure; Methacrylic acid (MAA), methyl methacrylate (MMA) analytical pure, the special chemical in Rui Jin, Tianjin company limited; Light trigger benzophenone analytical pure, Shanghai Ling Feng chemical reagent company limited, 2-hydroxy-2-methyl-1-phenyl-1-acetone (code name 1173), Shanghai Ling Feng chemical reagent company limited, analytical pure; Linking agent Viscoat 295 (code name TMPTA), sharp field, Nantong chemical industry company limited, analytical pure; Methylene dichloride, Concord, Tianjin Science and Technology Ltd., chromatographically pure; Glacial acetic acid, Shanghai phenanthrene reach industry and trade company limited and bridge branch office, analytical pure.
Instrument used herein: the ultra-violet lamp model is SB2100P/ F, 365 nm, 100 W, New York; Gas chromatograph, the GC 7890A of Agilent company.
Embodiment 1
In the reactor triangular flask, add successively 100.5mg thiophos, 145.1mg 4-vinylpridine and 26520mg methylene dichloride, behind 25 ℃ of lower vibration 1h, in 4 ℃ of refrigerators, place 12h.And then adding 2964mgTMPTA and 178.4mg light trigger, mix, inflated with nitrogen 2min in the reactor, then vacuumize and reactor is sealed, reactor placed ice-water bath and regulate ultraviolet lamp tube and the distance of ice-water bath underwater reactor is 7 cm, make reaction system carry out photopolymerization reaction.Behind the reaction 2h, pulverizing, grind after the block product of gained taken out, is 9/1 methyl alcohol/acetic acid solvent extracting with volume ratio, and vacuum-drying obtains thiophos molecularly imprinted polymer 2568mg.
Comparative Examples 1:
Absorption property for the thiophos molecularly imprinted polymer of verifying embodiments of the invention 1 gained has prepared blank polymkeric substance in the situation that do not add thiophos, and other operations when preparing blank polymkeric substance are all undertaken by embodiment 1.
The absorption property test
Accurately take by weighing respectively the thiophos molecularly imprinted polymer of 25.0 mg embodiment, 1 preparation and the blank polymkeric substance of Comparative Examples 1 preparation, it is dissolved in thiophos content is respectively 0.102,0.201,0.366,0.524,0.661,0.793,0.963 mmolL
1One be assembled with in the volumetric flask of 5.0 mL dichloromethane solutions, with vibration absorption 12 h under the volumetric flask room temperature, gc analysis is measured the Cf c of thiophos in the mentioned solution
e(mmolL
1), and Units of Account quality polymkeric substance is to the binding capacity q of thiophos
e(μ molg
1), with q
eTo c
eThe adsorption isotherm line chart is drawn in mapping, carries out match with the Langmuir isotherm formula, calculates polymkeric substance to the saturated extent of adsorption q of thiophos
m
The saturated extent of adsorption of thiophos molecularly imprinted polymer is 600.7 μ molg
1, the saturated extent of adsorption 104.9 μ molg of blank polymkeric substance
1, the saturated extent of adsorption of thiophos molecularly imprinted polymer is apparently higher than the saturated extent of adsorption of blank polymkeric substance.
Detect the test of organophosphorus in the water
1, sample liquid preparation
A), the thiophos molecularly imprinted polymer that utilizes embodiment 1 to prepare detects the examination of the organophosphorus in the water
Test, the present embodiment adopts solid phase extraction to prepare sample liquid.
Take by weighing the thiophos molecularly imprinted polymer of 50.0 mg embodiment, 1 preparation, it as solid phase extraction column stuffing, is used first methyl alcohol 10mL Continuous leaching solid-phase extraction column 2 times (filling with post 2 times), use again high purity water 10mL Continuous leaching solid-phase extraction column 2 times.Get water sample 250mL to be detected, filter through Φ 60 millipore filtrations (mixed cellulose ester), filtrate flows in the reagent bottle.Take advantage of solid-phase extraction column when not dried, filtrate is poured into make its enrichment filtrate in the solid-phase extraction column, simultaneously with 10mLmin
1Flow suction filtration solid-phase extraction column.Then, with 5mL distilled water wash pillar, water is drained.Take methylene dichloride as elutriant, wash-out above-mentioned solid phase column extractor, methylene dichloride under action of gravity the nature lower, make it the organophosphorus in the abundant desorb filtrate, collect at last elutriant in the concentrated purging bottle in the point end, and under room temperature with Nitrogen evaporator solution being dried up, again with methylene dichloride will purge the bottle constant volume be 1.0mL, treat chromatographic determination.
B), adopt traditional solvent extraction method to prepare sample liquid (Comparative Examples 2).
When adopting traditional solvent extraction method, get 250mL water sample to be detected, place the 500mL separating funnel, extract at twice with the 50mL methylene dichloride, merge twice extraction liquid, extraction liquid is concentrated into 1.0mL behind anhydrous sodium sulfate dehydration, for analyzing.
2, gas-chromatography arranges condition
Gas-chromatography adopts HP-5 capillary column (30 m * 0. 32 mm * 0. 25 μ m); Used carrier gas is high pure nitrogen; Injector temperature is made as 220 ℃; Detector (ECD) temperature is made as 300 ℃; Adopt temperature programming: keep 1min during 80 ℃ of starting temperatures, first with 30 ℃ of min
-1Temperature rise rate rise to 180 ℃, then with 5 ℃ of min
-1Temperature rise rate rises to 250 ℃; Carrier gas flux is made as 1.0mLmin
-1The make-up gas flow is made as 60mLmin
-1Splitless injecting samples; External standard method is quantitative.
With a), b), two kinds of sample liquid that method makes, detect the organophosphorus index with above-mentioned vapor-phase chromatography respectively, the index that detects comprises minimum detectable concentration, tolerance range RSD and recovery of standard addition, the comparative result of each index sees Table 1.The result can find out, molecular engram solid phase extraction is low than the solvent extraction detection limit, and RSD is suitable with average recovery of standard addition effect.Illustrate that utilization thiophos molecular engram solid phase extraction is better to the concentration and separation effect of organophosphorus, the method for foundation accurately and reliably.Fig. 1 is that the prepared thiophos molecularly imprinted polymer of the present embodiment is used for organophosphorous pesticides method detection organophosphorus pesticide reference colour spectrogram, Fig. 2 is that Comparative Examples 2 solvent extractions-vapor-phase chromatography detects the organophosphorus pesticide gas chromatogram, Fig. 1 does not have impurity peaks, illustrates that the molecular recognition of molecular engram solid phase extraction is effective.
The detection limit of two kinds of different extracting process of table 1 and RSD are relatively
Embodiment 2
The difference of the present embodiment and embodiment 1 is:
Change monomer among the embodiment 1 into 50mg MMA, the consumption of linking agent TMPTA changes 1025mg into, and the consumption of light trigger changes 105mg into, reaction times changes 0.5h into, ultraviolet lamp tube is 11 cm from the distance of reactor, and other operation is all undertaken by embodiment 1, consists of embodiment 2.
Embodiment 3
The difference of the present embodiment and embodiment 1 is:
With thiophos changes 115mg among the embodiment 1, monomer changes 325mgMA into, dosage of crosslinking agent changes 5 241mg into, and the light trigger consumption changes 452mg into, reaction times changes 1.5h into, ultraviolet lamp is 3cm from the distance of reactor, and other operation is all undertaken by embodiment 1, consists of embodiment 3.
Embodiment 4
The difference of the present embodiment and embodiment 1 is:
With thiophos consumption among the embodiment 1 change 104mg into, monomer changes 276mg MMA into, dosage of crosslinking agent changes 3154mg into, the light trigger consumption changes 216mg into, ultraviolet lamp is 9cm from the distance of reactor, other operation is all undertaken by embodiment 1, consists of embodiment 4.
The saturated extent of adsorption of embodiment of the invention 2-4 sees Table 2.
The saturated extent of adsorption q of table 2 embodiment 1-4
m/ (μ molg
1)
The minimum detectable concentration of embodiment of the invention 2-4 sees Table 3.
The minimum detectability ρ of table 3 embodiment 1-4/(μ gL
-1)
Claims (5)
1. one kind prepares the method that the thiophos molecularly imprinted polymer is used in water quality detection, it is characterized in that: the method is take thiophos as template molecule, the thiophos molecularly imprinted polymer that is fit to detect in the water surrounding organophosphorus by the uv-light polymerization preparation, concrete preparation process is as follows:
1) in reactor, adds successively thiophos, monomer and dichloromethane solvent, at 25 ℃ of lower vibration 1h; Then in 4 ℃ environment, place 12h;
2) add linking agent Viscoat 295 and light trigger in the above-mentioned reaction system, mix, then inflated with nitrogen 2min in the reactor vacuumizes sealing again;
3) above-mentioned reactor is placed ice-water bath and regulate UV-light and the distance of ice-water bath underwater reactor, make reaction system carry out photopolymerization reaction, the reaction times is 0.5～2.5h;
4) block product with gained takes out rear pulverizing, grinds, and is that methyl alcohol/acetic acid solvent of 9/1 carries out extracting to product with volume ratio, and vacuum-drying obtains the thiophos molecularly imprinted polymer.
2. according to claim 1ly a kind ofly prepare water quality detection with the method for thiophos molecularly imprinted polymer, it is characterized in that: the parts by weight of each material are in the described reaction system: 1 part of thiophos, monomer 0.5-3 part, 260 parts of methylene dichloride, Viscoat 295 10-50 part, light trigger 1-4 part.
3. according to claim 1ly a kind ofly prepare water quality detection with the method for thiophos molecularly imprinted polymer, it is characterized in that: described light trigger is that mass ratio is the benzophenone of 1:1 and the mixture of 2-hydroxy-2-methyl-1-phenyl-1-acetone.
4. according to claim 1ly a kind ofly prepare water quality detection with the method for thiophos molecularly imprinted polymer, it is characterized in that: described monomer is any one of 4-vinylpridine, methyl methacrylate, methacrylic acid or acrylamide.
5. according to claim 1ly a kind ofly prepare water quality detection with the method for thiophos molecularly imprinted polymer, it is characterized in that: described UV-light is 3～11cm from the distance of reactor.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613758A (en) * | 2013-12-03 | 2014-03-05 | 江南大学 | Automatic-assembling method for preparing molecular imprint polyaniline nanocomposite |
| CN104677840A (en) * | 2013-11-29 | 2015-06-03 | 中国科学院烟台海岸带研究所 | Method for detecting benzo[alpha] pyrene with high sensitivity and selectivity |
| CN106947038A (en) * | 2017-04-07 | 2017-07-14 | 中国农业科学院农业质量标准与检测技术研究所 | Molecular imprinting stirring rod and preparation method thereof |
-
2012
- 2012-09-27 CN CN2012103689197A patent/CN102863586A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 刘静等: "《对硫磷分子印迹聚合物制备及其在水质检测中的应用》", 《分析试验室》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104677840A (en) * | 2013-11-29 | 2015-06-03 | 中国科学院烟台海岸带研究所 | Method for detecting benzo[alpha] pyrene with high sensitivity and selectivity |
| CN103613758A (en) * | 2013-12-03 | 2014-03-05 | 江南大学 | Automatic-assembling method for preparing molecular imprint polyaniline nanocomposite |
| CN103613758B (en) * | 2013-12-03 | 2016-05-11 | 江南大学 | Self-assembly method is prepared molecular engram polyaniline nano compound |
| CN106947038A (en) * | 2017-04-07 | 2017-07-14 | 中国农业科学院农业质量标准与检测技术研究所 | Molecular imprinting stirring rod and preparation method thereof |
| CN106947038B (en) * | 2017-04-07 | 2018-09-07 | 中国农业科学院农业质量标准与检测技术研究所 | Molecular imprinting stirring rod and preparation method thereof |
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Application publication date: 20130109 |