CN105254827A - Preparation method of magnetic nano molecularly imprinted polymer for separating nicotinic pesticide IPP - Google Patents

Preparation method of magnetic nano molecularly imprinted polymer for separating nicotinic pesticide IPP Download PDF

Info

Publication number
CN105254827A
CN105254827A CN201510811372.7A CN201510811372A CN105254827A CN 105254827 A CN105254827 A CN 105254827A CN 201510811372 A CN201510811372 A CN 201510811372A CN 105254827 A CN105254827 A CN 105254827A
Authority
CN
China
Prior art keywords
ratio
obtains
volume
magnetic nano
quality
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201510811372.7A
Other languages
Chinese (zh)
Other versions
CN105254827B (en
Inventor
杨鑫
张敏
张琬桐
王静
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harbin Institute of Technology
Original Assignee
Harbin Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Harbin Institute of Technology filed Critical Harbin Institute of Technology
Priority to CN201510811372.7A priority Critical patent/CN105254827B/en
Publication of CN105254827A publication Critical patent/CN105254827A/en
Application granted granted Critical
Publication of CN105254827B publication Critical patent/CN105254827B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Compounds Of Iron (AREA)

Abstract

The invention provides a preparation method of a magnetic nano molecularly imprinted polymer for separating a nicotinic pesticide IPP, aiming to solve the problem that methods for preparing magnetic nano molecularly imprinted polymers capable of separating the nicotinic pesticide IPP do not exist at present. The preparation method comprises the following steps: I. preparation of Fe3O4 magnetic nanoparticles; II. modification of the Fe3O4 magnetic nanoparticles; III. silanization of the Fe3O4 magnetic nanoparticles; IV. preparation of double bond modified Fe3O4@SiO2 particles; and V. preparation of the magnetic nano molecularly imprinted polymer for separating the nicotinic pesticide IPP. The preparation method has the beneficial effects that the maximum saturation adsorption quantity of the product towards IPP is 17.305+/-0.403mg/g and is 2.0 times that of a non-molecularly imprinted polymer; the adsorption quantity is still kept at about 85.3% after five-time repeated adsorption; and the repeated utilization rate is high.

Description

A kind of preparation method being separated the magnetic nanomolecules imprinted polymer of nicotine agricultural chemicals piperazine worm pyridine
Technical field
The present invention relates to a kind of preparation method being separated the molecularly imprinted polymer of nicotine agricultural chemicals piperazine worm pyridine.
Background technology
Piperazine worm pyridine (IPP) is the third generation nicotinic insecticide of China's independent research, chemical name is 1-((6-chloropyridine-3-base) methyl)-5-propoxy--7-methyl-8-nitro-1,2,3,5,6,7-six hydrogen imidazoles [1,2-a] pyridine, the control of the various crop insects such as fruit tree, grain, vegetables can be widely used in.A large amount of use can cause poisoning along with food chain enters human body, therefore needs extraction and isolation from food badly and goes out piperazine worm pyridine agricultural chemicals and carry out test and monitoring.But the farm crop matrix such as fruit, grain, vegetables is complicated, the composition that the interferometric analyses such as rich in proteins, carbohydrate, VITAMIN, pigment detect.Therefore the fast separating process of a kind of specific recognition piperazine worm pyridine is found for setting up accurately sensitive piperazine worm pyridine detection method, guaranteeing that food safety is significant.
Magnetic Nano surface molecule print technology is that the quick identification separation of piperazine worm pyridine agricultural chemicals provides new approaches.Namely conventional molecular imprinted polymer is polymerized rear eluted template molecule in a solvent by template molecule, function monomer, linking agent and initiator, has the rigid polymer with particular space structure hole of template molecule with obtained " trace ".Molecular imprinted polymer on surface is at carrier surface polymerizable molecular imprinted layer, make action site be positioned at carrier particle surface or near surface, not only reduce embedding phenomenon, and reduce non-specific adsorption, make binding ability higher, also have rate of mass transfer and Geng Gao recognition efficiency faster.There is the large magnetic nano-particle of magnetic, good dispersity, specific surface area for carrier, the pyridine of nicotine agricultural chemicals piperazine worm is that the magnetic nano surface molecular imprinted polymer of template molecule combines advanced magnetic Nano technology and surface molecule print technology, can identify the piperazine worm pyridine pesticide residue isolated in food fast and accurately from complicated food substrate.
At present, the separation method adopting magnetic nanomolecules trace to carry out the pyridine of novel nicotine agricultural chemicals piperazine worm has no report.
Thus, prepare a kind of magnetic nanomolecules imprinted polymer being separated the pyridine of piperazine worm, so that it is necessary for isolating the pyridine of piperazine worm fast, accurately and efficiently.
Summary of the invention
The present invention does not prepare the problem of the method for the magnetic nanomolecules imprinted polymer of separable nicotine agricultural chemicals piperazine worm pyridine at present in order to solve, and provides a kind of preparation method being separated the magnetic nanomolecules imprinted polymer of nicotine agricultural chemicals piperazine worm pyridine.
A kind of preparation method being separated the magnetic nanomolecules imprinted polymer of nicotine agricultural chemicals piperazine worm pyridine of the present invention carries out according to the following steps:
One, Fe is prepared 3o 4magnetic nano-particle: iron trichloride is dissolved in ethylene glycol, supersound process is to existing without solid, then anhydrous sodium acetate is added, low whipping speed is stir 25min ~ 35min under the condition of 400r/min ~ 600r/min, be transferred in reactor, be react 11h ~ 13h under the condition of 180 ~ 220 DEG C in temperature, stopped reaction, leave standstill 15min ~ 25min, then magneticseparation sedimentation is carried out with ndfeb magnet, after pouring out supernatant liquid, carrying out washing treatment is carried out to the solid matter obtained, then be vacuum-drying 5h ~ 7h under the condition of 40 ~ 50 DEG C in temperature by material after washing, obtain Fe 3o 4magnetic nano-particle, described carrying out washing treatment process is as follows: 1. use the washing with alcohol solid matter of 95%, then carries out magneticseparation sedimentation with ndfeb magnet, obtains solid product after pouring out supernatant liquid, 2. repeating step 1. 3 times, 3. use distilled water washed solid, then carry out magneticseparation sedimentation with ndfeb magnet, after pouring out supernatant liquid, obtain solid product, 4. repeating step 3. 3 times,
The quality of described iron trichloride is 13.5g:(450 ~ 550 with the ratio of the volume of ethylene glycol) mL; Described iron trichloride and the mass ratio of anhydrous sodium acetate are 13.5:(35 ~ 37);
The ethanol of each carrying out washing treatment used 95% and the volume ratio of ethylene glycol are 1:(4.5 ~ 5.5); The volume ratio of each carrying out washing treatment institute's distilled water and ethylene glycol is 1:(4.5 ~ 5.5);
Two, Fe 3o 4the modification of magnetic nano-particle; To the Fe that step one obtains 3o 4add hydrochloric acid and trisodium citrate in magnetic nano-particle, supersound process 15min ~ 25min, be then vacuum-drying 5h ~ 7h under the condition of 40 ~ 50 DEG C in temperature, complete modification, obtain the Fe being with identical charges 3o 4magnetic nano-particle;
The Fe that described step one obtains 3o 4the quality of magnetic nano-particle is 0.4g:(12 ~ 18 with the ratio of the volume of hydrochloric acid) mL; The Fe that described step one obtains 3o 4the quality of magnetic nano-particle is 0.4g:(12 ~ 18 with the ratio of the volume of trisodium citrate) mL;
Three, Fe 3o 4the silanization of magnetic nano-particle: to the Fe of the band identical charges that step 2 obtains 3o 4virahol and distilled water is added in magnetic nano-particle, supersound process is to being uniformly dispersed, then be that 1.8mL/min ~ 2.3mL/min dropwise adds ammoniacal liquor with rate of addition, after dropwising, be that 1.8mL/min ~ 2.3mL/min dropwise adds tetraethoxy again with rate of addition, after dropwising, be that 400r/min ~ 600r/min stirs 10h ~ 14h with stirring velocity under room temperature, then magneticseparation sedimentation is carried out with ndfeb magnet, after pouring out supernatant liquid, carrying out washing treatment is carried out to the solid matter obtained, then be vacuum-drying 5h ~ 7h under the condition of 40 ~ 50 DEG C in temperature by material after washing, complete silylating reagent, obtain Fe 3o 4siO 2particulate, described carrying out washing treatment process is as follows: 1. use the washing with alcohol solid matter of 95%, then carries out magneticseparation sedimentation with ndfeb magnet, obtains solid product after pouring out supernatant liquid, 2. repeating step 1. 3 times, 3. use deionized water wash solid matter, then carry out magneticseparation sedimentation with ndfeb magnet, after pouring out supernatant liquid, obtain solid product, 4. repeating step 3. 3 times,
The Fe of the band identical charges that described step 2 obtains 3o 4the quality of magnetic nano-particle is 0.4g:(80 ~ 120 with the ratio of the volume of Virahol) mL; The Fe of the band identical charges that described step 2 obtains 3o 4the quality of magnetic nano-particle is 0.4g:(7 ~ 9 with the ratio of the volume of distilled water) mL; The Fe of the band identical charges that described step 2 obtains 3o 4the quality of magnetic nano-particle is 0.4g:(4 ~ 6 with the ratio of the volume of ammoniacal liquor) mL; The Fe of the band identical charges that described step 2 obtains 3o 4the quality of magnetic nano-particle is 0.4g:(0.8 ~ 1.2 with the ratio of the volume of tetraethoxy) mL;
The ethanol of each carrying out washing treatment used 95% and the volume ratio of Virahol are 1:(0.8 ~ 1.2); The volume ratio of each carrying out washing treatment deionized water used and Virahol is 1:(0.8 ~ 1.2);
Four, double bond modifies Fe 3o 4siO 2the preparation of particulate: the Fe that step 3 is obtained 3o 4siO 2particulate, 3-(trimethoxysilyl) propyl acrylate, dry toluene and triethylamine mix; supersound process is to mixing; under nitrogen atmosphere protection; be stirring and refluxing 22h ~ 24h in the oil bath of 120 ~ 140 DEG C in temperature; magneticseparation sedimentation is carried out with ndfeb magnet after cooling; after pouring out supernatant liquid; carrying out washing treatment is carried out to the solid matter obtained; then be vacuum-drying 5h ~ 7h under the condition of 40 ~ 50 DEG C in temperature by material after washing; complete double bond graft modification, obtain Fe 3o 4siO 2c=C magnetic Nano microsphere; Described carrying out washing treatment process is as follows: 1. use toluene wash solid matter, then carries out magneticseparation sedimentation with ndfeb magnet, obtains solid product after pouring out supernatant liquid; 2. repeating step 1. 3 times; 3. use washing with alcohol solid matter, then carry out magneticseparation sedimentation with ndfeb magnet, after pouring out supernatant liquid, obtain solid product; 4. repeating step 3. 3 times;
The Fe that described step 3 obtains 3o 4siO 2the ratio of the volume of the quality of particulate and 3-(trimethoxysilyl) propyl acrylate is 0.4g:(3 ~ 5) mL; The Fe that described step 3 obtains 3o 4siO 2the quality of particulate is 0.4g:(90 ~ 110 with the ratio of the volume of dry toluene) mL; The Fe that described step 3 obtains 3o 4siO 2the quality of particulate is 0.4g:(1 ~ 3 with the ratio of the volume of triethylamine) mL;
The volume ratio of each carrying out washing treatment toluene used and dry toluene is 1:(0.8 ~ 1.2); The volume ratio of each carrying out washing treatment ethanol used and dry toluene is 1:(0.8 ~ 1.2);
Five, the preparation of the magnetic nanomolecules imprinted polymer of nicotine agricultural chemicals piperazine worm pyridine is separated: be dissolved in acetonitrile by the methacrylic acid of the pyridine of piperazine worm and 1.0mol/L, left at room temperature 10h ~ 14h, then add the Fe that step 4 obtains 3o 4siO 2c=C magnetic Nano microsphere, ethylene glycol dimethacrylate and Diisopropyl azodicarboxylate, be polyreaction 22h ~ 24h under the condition of 45 ~ 55 DEG C in temperature, leave standstill 15min ~ 25min, then magneticseparation sedimentation is carried out with ndfeb magnet, after pouring out supernatant liquid, with elutriant, wash-out is carried out to solid matter, be eluted to and detect without the pyridine of piperazine worm, namely obtain the magnetic nanomolecules imprinted polymer being separated the pyridine of novel nicotine agricultural chemicals piperazine worm;
The Fe that described step 4 obtains 3o 4siO 2the quality of C=C magnetic Nano microsphere and the mol ratio of piperazine worm pyridine are (35 ~ 45) mg:0.1mmol; The Fe that described step 4 obtains 3o 4siO 2ratio (35 ~ 45) mg:0.4mL of the quality of C=C magnetic Nano microsphere and the volume of the methacrylic acid of 1.0mol/L; The Fe that described step 4 obtains 3o 4siO 2ratio (35 ~ 45) mg:16.6mL of the quality of C=C magnetic Nano microsphere and the volume of acetonitrile; The Fe that described step 4 obtains 3o 4siO 2ratio (35 ~ 45) mg:1mL of the quality of C=C magnetic Nano microsphere and the volume of ethylene glycol dimethacrylate; The Fe that described step 4 obtains 3o 4siO 2ratio (35 ~ 45) mg:2mL of the quality of C=C magnetic Nano microsphere and the volume of Diisopropyl azodicarboxylate; Described elutriant is the mixed solution of methyl alcohol and acetic acid, and in elutriant, the volume ratio of methyl alcohol and acetic acid is 9:1.
The invention discloses a kind of method preparing the pyridine of magnetic molecularly imprinted technology separation nicotine agricultural chemicals piperazine worm, first to Fe 3o 4carry out silanization, then use 3-(trimethoxysilyl) propyl acrylate to the Fe of synthesis 3o 4siO 2carry out the Fe that modification generates double bond grafting 3o 4siO2C=C, then with piperazine worm pyridine (IPP) be template, Diisopropyl azodicarboxylate (AIBN) is initiator, methacrylic acid (MAA) is function monomer, ethylene glycol dimethacrylate (EGDMA) for linking agent, with Fe 3o 4siO 2c=C is that carrier obtains piperazine worm pyridine magnetic nanomolecules imprinted polymer.Compensate for and there is no a kind of cavity that can be separated the molecularly imprinted polymer of piperazine worm pyridine at present, the maximum saturation adsorptive capacity of magnetic nanomolecules imprinted polymer to the pyridine of piperazine worm of the separation obtained novel nicotine agricultural chemicals piperazine worm pyridine is 17.305 ± 0.403mg/g, it is 2.0 times of non-molecular imprinting maximum saturation adsorptive capacity, adsorption efficiency is high, absorption is repeated through five times, adsorptive capacity does not have considerable change, Fe 3o 4siO 2the adsorptive capacity of C=C-MIP reduces by 12.45%, but still remains on about 85.3%, and repeating utilization factor is high, can be applicable to be separated piperazine worm pyridine field.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the magnetic nanomolecules imprinted polymer of the separation novel nicotine agricultural chemicals piperazine worm pyridine of test one;
Fig. 2 is the infrared spectra spectrogram of the magnetic nanomolecules imprinted polymer of the separation novel nicotine agricultural chemicals piperazine worm pyridine of test one;
Fig. 3 is the XRD figure of the magnetic nanomolecules imprinted polymer of the separation novel nicotine agricultural chemicals piperazine worm pyridine of test one;
Fig. 4 is that the magnetic nanomolecules imprinted polymer of the separation novel nicotine agricultural chemicals piperazine worm pyridine of test one is to the adsorptive capacity-time plot of piperazine worm pyridine; Wherein a is Fe 3o 4siO 2c=C-MIPs, b are Fe 3o 4siO 2c=C-NIPs;
Fig. 5 is the canonical plotting measuring piperazine worm pyridine absorbancy;
Fig. 6 is the repeating utilization factor column diagram of the magnetic nanomolecules imprinted polymer of the separation novel nicotine agricultural chemicals piperazine worm pyridine of test one;
Fig. 7 is the magnetic nanomolecules imprinted polymer selective recognition ability column diagram of the separation novel nicotine agricultural chemicals piperazine worm pyridine of test one; Wherein for Fe 3o 4siO 2c=C-MIPs, for Fe 3o 4siO 2c=C-NIPs.
Embodiment
Technical scheme of the present invention is not limited to following embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: a kind of preparation method being separated the magnetic nanomolecules imprinted polymer of nicotine agricultural chemicals piperazine worm pyridine of present embodiment carries out according to the following steps:
One, Fe is prepared 3o 4magnetic nano-particle: iron trichloride is dissolved in ethylene glycol, supersound process is to existing without solid, then anhydrous sodium acetate is added, low whipping speed is stir 25min ~ 35min under the condition of 400r/min ~ 600r/min, be transferred in reactor, be react 11h ~ 13h under the condition of 180 ~ 220 DEG C in temperature, stopped reaction, leave standstill 15min ~ 25min, then magneticseparation sedimentation is carried out with ndfeb magnet, after pouring out supernatant liquid, carrying out washing treatment is carried out to the solid matter obtained, then be vacuum-drying 5h ~ 7h under the condition of 40 ~ 50 DEG C in temperature by material after washing, obtain Fe 3o 4magnetic nano-particle, described carrying out washing treatment process is as follows: 1. use the washing with alcohol solid matter of 95%, then carries out magneticseparation sedimentation with ndfeb magnet, obtains solid product after pouring out supernatant liquid, 2. repeating step 1. 3 times, 3. use distilled water washed solid, then carry out magneticseparation sedimentation with ndfeb magnet, after pouring out supernatant liquid, obtain solid product, 4. repeating step 3. 3 times,
The quality of described iron trichloride is 13.5g:(450 ~ 550 with the ratio of the volume of ethylene glycol) mL; Described iron trichloride and the mass ratio of anhydrous sodium acetate are 13.5:(35 ~ 37);
The ethanol of each carrying out washing treatment used 95% and the volume ratio of ethylene glycol are 1:(4.5 ~ 5.5); The volume ratio of each carrying out washing treatment institute's distilled water and ethylene glycol is 1:(4.5 ~ 5.5);
Two, Fe 3o 4the modification of magnetic nano-particle; To the Fe that step one obtains 3o 4add hydrochloric acid and trisodium citrate in magnetic nano-particle, supersound process 15min ~ 25min, be then vacuum-drying 5h ~ 7h under the condition of 40 ~ 50 DEG C in temperature, complete modification, obtain the Fe being with identical charges 3o 4magnetic nano-particle;
The Fe that described step one obtains 3o 4the quality of magnetic nano-particle is 0.4g:(12 ~ 18 with the ratio of the volume of hydrochloric acid) mL; The Fe that described step one obtains 3o 4the quality of magnetic nano-particle is 0.4g:(12 ~ 18 with the ratio of the volume of trisodium citrate) mL;
Three, Fe 3o 4the silanization of magnetic nano-particle: to the Fe of the band identical charges that step 2 obtains 3o 4virahol and distilled water is added in magnetic nano-particle, supersound process is to being uniformly dispersed, then be that 1.8mL/min ~ 2.3mL/min dropwise adds ammoniacal liquor with rate of addition, after dropwising, be that 1.8mL/min ~ 2.3mL/min dropwise adds tetraethoxy again with rate of addition, after dropwising, be that 400r/min ~ 600r/min stirs 10h ~ 14h with stirring velocity under room temperature, then magneticseparation sedimentation is carried out with ndfeb magnet, after pouring out supernatant liquid, carrying out washing treatment is carried out to the solid matter obtained, then be vacuum-drying 5h ~ 7h under the condition of 40 ~ 50 DEG C in temperature by material after washing, complete silylating reagent, obtain Fe 3o 4siO 2particulate, described carrying out washing treatment process is as follows: 1. use the washing with alcohol solid matter of 95%, then carries out magneticseparation sedimentation with ndfeb magnet, obtains solid product after pouring out supernatant liquid, 2. repeating step 1. 3 times, 3. use deionized water wash solid matter, then carry out magneticseparation sedimentation with ndfeb magnet, after pouring out supernatant liquid, obtain solid product, 4. repeating step 3. 3 times,
The Fe of the band identical charges that described step 2 obtains 3o 4the quality of magnetic nano-particle is 0.4g:(80 ~ 120 with the ratio of the volume of Virahol) mL; The Fe of the band identical charges that described step 2 obtains 3o 4the quality of magnetic nano-particle is 0.4g:(7 ~ 9 with the ratio of the volume of distilled water) mL; The Fe of the band identical charges that described step 2 obtains 3o 4the quality of magnetic nano-particle is 0.4g:(4 ~ 6 with the ratio of the volume of ammoniacal liquor) mL; The Fe of the band identical charges that described step 2 obtains 3o 4the quality of magnetic nano-particle is 0.4g:(0.8 ~ 1.2 with the ratio of the volume of tetraethoxy) mL;
The ethanol of each carrying out washing treatment used 95% and the volume ratio of Virahol are 1:(0.8 ~ 1.2); The volume ratio of each carrying out washing treatment deionized water used and Virahol is 1:(0.8 ~ 1.2);
Four, double bond modifies Fe 3o 4siO 2the preparation of particulate: the Fe that step 3 is obtained 3o 4siO 2particulate, 3-(trimethoxysilyl) propyl acrylate, dry toluene and triethylamine mix; supersound process is to mixing; under nitrogen atmosphere protection; be stirring and refluxing 22h ~ 24h in the oil bath of 120 ~ 140 DEG C in temperature; magneticseparation sedimentation is carried out with ndfeb magnet after cooling; after pouring out supernatant liquid; carrying out washing treatment is carried out to the solid matter obtained; then be vacuum-drying 5h ~ 7h under the condition of 40 ~ 50 DEG C in temperature by material after washing; complete double bond graft modification, obtain Fe 3o 4siO 2c=C magnetic Nano microsphere; Described carrying out washing treatment process is as follows: 1. use toluene wash solid matter, then carries out magneticseparation sedimentation with ndfeb magnet, obtains solid product after pouring out supernatant liquid; 2. repeating step 1. 3 times; 3. use washing with alcohol solid matter, then carry out magneticseparation sedimentation with ndfeb magnet, after pouring out supernatant liquid, obtain solid product; 4. repeating step 3. 3 times;
The Fe that described step 3 obtains 3o 4siO 2the ratio of the volume of the quality of particulate and 3-(trimethoxysilyl) propyl acrylate is 0.4g:(3 ~ 5) mL; The Fe that described step 3 obtains 3o 4siO 2the quality of particulate is 0.4g:(90 ~ 110 with the ratio of the volume of dry toluene) mL; The Fe that described step 3 obtains 3o 4siO 2the quality of particulate is 0.4g:(1 ~ 3 with the ratio of the volume of triethylamine) mL;
The volume ratio of each carrying out washing treatment toluene used and dry toluene is 1:(0.8 ~ 1.2); The volume ratio of each carrying out washing treatment ethanol used and dry toluene is 1:(0.8 ~ 1.2);
Five, the preparation of the magnetic nanomolecules imprinted polymer of nicotine agricultural chemicals piperazine worm pyridine is separated: be dissolved in acetonitrile by the methacrylic acid of the pyridine of piperazine worm and 1.0mol/L, left at room temperature 10h ~ 14h, then add the Fe that step 4 obtains 3o 4siO 2c=C magnetic Nano microsphere, ethylene glycol dimethacrylate and Diisopropyl azodicarboxylate, be polyreaction 22h ~ 24h under the condition of 45 ~ 55 DEG C in temperature, leave standstill 15min ~ 25min, then magneticseparation sedimentation is carried out with ndfeb magnet, after pouring out supernatant liquid, with elutriant, wash-out is carried out to solid matter, be eluted to and detect without the pyridine of piperazine worm, namely obtain the magnetic nanomolecules imprinted polymer being separated the pyridine of novel nicotine agricultural chemicals piperazine worm;
The Fe that described step 4 obtains 3o 4siO 2the quality of C=C magnetic Nano microsphere and the mol ratio of piperazine worm pyridine are (35 ~ 45) mg:0.1mmol; The Fe that described step 4 obtains 3o 4siO 2ratio (35 ~ 45) mg:0.4mL of the quality of C=C magnetic Nano microsphere and the volume of the methacrylic acid of 1.0mol/L; The Fe that described step 4 obtains 3o 4siO 2ratio (35 ~ 45) mg:16.6mL of the quality of C=C magnetic Nano microsphere and the volume of acetonitrile; The Fe that described step 4 obtains 3o 4siO 2ratio (35 ~ 45) mg:1mL of the quality of C=C magnetic Nano microsphere and the volume of ethylene glycol dimethacrylate; The Fe that described step 4 obtains 3o 4siO 2ratio (35 ~ 45) mg:2mL of the quality of C=C magnetic Nano microsphere and the volume of Diisopropyl azodicarboxylate; Described elutriant is the mixed solution of methyl alcohol and acetic acid, and in elutriant, the volume ratio of methyl alcohol and acetic acid is 9:1.
Embodiment two: present embodiment and embodiment one unlike: the quality of the iron trichloride described in step one is 13.5g:500mL with the ratio of the volume of ethylene glycol; The mass ratio of the iron trichloride described in step one and anhydrous sodium acetate is 13.5:36.Other step is identical with embodiment one with parameter.
Embodiment three: present embodiment and embodiment one or two are unlike the Fe that the step one described in step 2 obtains 3o 4the quality of magnetic nano-particle is 0.4g:15mL with the ratio of the volume of hydrochloric acid; The Fe that step one described in step 2 obtains 3o 4the quality of magnetic nano-particle is 0.4g:15mL with the ratio of the volume of trisodium citrate.Other step is identical with embodiment one or two with parameter.
Embodiment four: one of present embodiment and embodiment one to three unlike: the concentration of the hydrochloric acid described in step 2 is 2mol/L.Other step is identical with one of parameter and embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: the concentration of the trisodium citrate described in step 2 is 0.5mol/L.Other step is identical with one of parameter and embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five are unlike the Fe of the band identical charges that the step 2 described in step 3 obtains 3o 4the quality of magnetic nano-particle is 0.4g:100mL with the ratio of the volume of Virahol.The Fe of the band identical charges that the step 2 described in step 3 obtains 3o 4the quality of magnetic nano-particle is 0.4g:8mL with the ratio of the volume of distilled water; The Fe of the band identical charges that the step 2 described in step 3 obtains 3o 4the quality of magnetic nano-particle is 0.4g:5mL with the ratio of the volume of ammoniacal liquor; The Fe of the band identical charges that the step 2 described in step 3 obtains 3o 4the quality of magnetic nano-particle is 0.4g:1mL with the ratio of the volume of ammoniacal liquor.Other step is identical with one of parameter and embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six are unlike Fe that the step 3 described in step 4 obtains 3o 4siO 2the ratio of the volume of the quality of particulate and 3-(trimethoxysilyl) propyl acrylate is 0.4g:4mL; The Fe that step 3 described in step 4 obtains 3o 4siO 2the quality of particulate is 0.4g:100mL with the ratio of the volume of dry toluene; The Fe that step 3 described in step 4 obtains 3o 4siO 2the quality of particulate is 0.4g:2mL with the ratio of the volume of triethylamine.Other step is identical with one of parameter and embodiment one to six.
Embodiment eight: one of one of present embodiment and embodiment one to seven are unlike Fe that the step 4 described in step 5 obtains 3o 4siO 2the quality of C=C magnetic Nano microsphere and the mol ratio of piperazine worm pyridine are 40mg:0.1mmol; The Fe that step 4 described in step 5 obtains 3o 4siO 2the ratio 40mg:0.4mL of the quality of C=C magnetic Nano microsphere and the volume of the methacrylic acid of 1.0mol/L; The Fe that step 4 described in step 5 obtains 3o 4siO 2the ratio 40mg:16.6mL of the quality of C=C magnetic Nano microsphere and the volume of acetonitrile; The Fe that step 4 described in step 5 obtains 3o 4siO 2the ratio 40mg:1mL of the quality of C=C magnetic Nano microsphere and the volume of ethylene glycol dimethacrylate; The Fe that step 4 described in step 5 obtains 3o 4siO 2the ratio 40mg:2mL of the quality of C=C magnetic Nano microsphere and the volume of Diisopropyl azodicarboxylate.Other step is identical with one of parameter and embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight unlike: the concentration of the ethylene glycol dimethacrylate described in step 5 is 1mol/L.Other step is identical with one of parameter and embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine unlike: the concentration of the Diisopropyl azodicarboxylate described in step 5 is 10mg/mL.Other step is identical with one of parameter and embodiment one to nine.
With following verification experimental verification beneficial effect of the present invention:
Test one, a kind of preparation method being separated the magnetic nanomolecules imprinted polymer of nicotine agricultural chemicals piperazine worm pyridine carry out according to the following steps:
One, Fe is prepared 3o 4magnetic nano-particle: the iron trichloride of 13.5g is dissolved in the ethylene glycol of 500mL, supersound process is to existing without solid, then the anhydrous sodium acetate of 36g is added, low whipping speed is stir 30min under the condition of 500r/min, be transferred in reactor, be react 12h under the condition of 200 DEG C in temperature, stopped reaction, leave standstill 20min, then carry out magneticseparation sedimentation with ndfeb magnet, after pouring out supernatant liquid, carrying out washing treatment is carried out to the solid matter obtained, then be vacuum-drying 6h under the condition of 45 DEG C in temperature by material after washing, obtain Fe 3o 4magnetic nano-particle; Described carrying out washing treatment process is as follows: the washing with alcohol solid matter 1. using 95% of 100mL, then carries out magneticseparation sedimentation with ndfeb magnet, obtains solid product after pouring out supernatant liquid; 2. repeating step 1. 3 times; 3. use the distilled water washed solid of 100mL, then carry out magneticseparation sedimentation with ndfeb magnet, after pouring out supernatant liquid, obtain solid product; 4. repeating step 3. 3 times;
Two, Fe 3o 4the modification of magnetic nano-particle; To the Fe that 0.4g step one obtains 3o 4add the hydrochloric acid of 15mL and the trisodium citrate of 15mL in magnetic nano-particle, supersound process 20min, be then vacuum-drying 6h under the condition of 45 DEG C in temperature, complete modification, obtain the Fe being with identical charges 3o 4magnetic nano-particle;
Three, Fe 3o 4the silanization of magnetic nano-particle: to the Fe of the band identical charges that 0.4g step 2 obtains 3o 4the Virahol of 100mL and the distilled water of 8mL is added in magnetic nano-particle, supersound process is to being uniformly dispersed, then be the ammoniacal liquor that 2mL/min dropwise adds 5mL with rate of addition, after dropwising, be the tetraethoxy that 2mL/min dropwise adds 1mL again with rate of addition, after dropwising, be that 500r/min stirs 12h with stirring velocity under room temperature, then magneticseparation sedimentation is carried out with ndfeb magnet, after pouring out supernatant liquid, carrying out washing treatment is carried out to the solid matter obtained, then be vacuum-drying 6h under the condition of 45 DEG C in temperature by material after washing, complete silylating reagent, obtain Fe 3o 4siO 2particulate, described carrying out washing treatment process is as follows: the washing with alcohol solid matter 1. using 95% of 100mL, then carries out magneticseparation sedimentation with ndfeb magnet, obtains solid product after pouring out supernatant liquid, 2. repeating step 1. 3 times, 3. use the deionized water wash solid matter of 100mL, then carry out magneticseparation sedimentation with ndfeb magnet, after pouring out supernatant liquid, obtain solid product, 4. repeating step 3. 3 times,
Four, double bond modifies Fe 3o 4siO 2particulate: the Fe that 0.4g step 3 is obtained 3o 4siO 2the triethylamine mixing of 3-(trimethoxysilyl) propyl acrylate of particulate, 4mL, the dry toluene of 100mL and 2mL; supersound process is to mixing; under nitrogen atmosphere protection; be stirring and refluxing 24h in the oil bath of 130 DEG C in temperature; magneticseparation sedimentation is carried out with ndfeb magnet after cooling; after pouring out supernatant liquid; carrying out washing treatment is carried out to the solid matter obtained; then be vacuum-drying 6h under the condition of 45 DEG C in temperature by material after washing; complete double bond graft modification, obtain Fe 3o 4siO 2c=C magnetic Nano microsphere; Described carrying out washing treatment process is as follows: the toluene wash solid matter 1. using 100mL, then carries out magneticseparation sedimentation with ndfeb magnet, obtains solid product after pouring out supernatant liquid; 2. repeating step 1. 3 times; 3. use the washing with alcohol solid matter of 100mL, then carry out magneticseparation sedimentation with ndfeb magnet, after pouring out supernatant liquid, obtain solid product; 4. repeating step 3. 3 times;
Five, the preparation of the magnetic nanomolecules imprinted polymer of nicotine agricultural chemicals piperazine worm pyridine is separated: be dissolved in the acetonitrile of 16.6mL by the methacrylic acid of the piperazine worm pyridine of 0.1mmol and the 1.0mol/L of 0.4mL, left at room temperature 12h, the Fe that the step 4 then adding 40mg obtains 3o 4siO 2the ethylene glycol dimethacrylate of C=C magnetic Nano microsphere, 1mL and the Diisopropyl azodicarboxylate of 2mL, be polyreaction 24h under the condition of 50 DEG C in temperature, leave standstill 20min, then magneticseparation sedimentation is carried out with ndfeb magnet, after pouring out supernatant liquid, with elutriant, wash-out is carried out to solid matter, be eluted to and detect without the pyridine of piperazine worm, namely obtain the magnetic nanomolecules imprinted polymer being separated the pyridine of novel nicotine agricultural chemicals piperazine worm;
Described elutriant is the mixed solution of methyl alcohol and acetic acid, and in elutriant, the volume ratio of methyl alcohol and acetic acid is 9:1.
(1), scanning electron microscope detection is carried out to the magnetic nanomolecules imprinted polymer of the separation of test one novel nicotine agricultural chemicals piperazine worm pyridine, result as shown in Figure 1, as seen from Figure 1, the magnetic nanomolecules imprinted polymer surface irregularity of the separation novel nicotine agricultural chemicals piperazine worm pyridine of test one is rough, there is adhesion phenomenon in part magnetic molecularly imprinted polymer microballoon, and there is on magnetic molecularly imprinted polymer surface the cavity that form differs, being successfully prepared of molecularly imprinted polymer has been described.
(2), infrared spectra detection is carried out to the magnetic nanomolecules imprinted polymer of the separation of test one novel nicotine agricultural chemicals piperazine worm pyridine, obtain the infrared spectra spectrogram of the magnetic nanomolecules imprinted polymer of the separation novel nicotine agricultural chemicals piperazine worm pyridine of test one as shown in Figure 2, as can be seen from Figure 2 at 582cm -1having there is the stretching vibration peak of Fe-O in place, is Fe 3o 4characteristic peak, show to successfully synthesize Fe 3o 4particle.Due to Fe 3o 4magnetic particle core is coated on nexine, so its characteristic absorption peaks is more weak.1091cm -1the absorption peak at place is the stretching vibration peak of Si-O-Si, 958cm -1place is the stretching vibration peak of Si-O-H, 800cm -1place is the stretching vibration peak of Si-O, 466cm -1place is the stretching vibration peak of O-Si-O, and these characteristic peaks are all SiO 2principal character absorption peak, indicate Fe 3o 4silane surface is combined to successfully.1731cm -1place is the charateristic avsorption band of ester carbonyl group, is the characteristic peak of 3-(trimethoxysilyl) propyl acrylate, shows successfully grafting double bond.2952cm -1place is obvious saturated C-H stretching vibration absorption peak, 1456cm -1and 1390cm -1for C-C charateristic avsorption band, show Fe 3o 4siO 2containing ethylene glycol dimethacrylate (EDGMA) modular construction repeated in C=C-MIP, illustrate that molecularly imprinted polymer synthesizes successfully.。
(3), X-ray diffraction sign is carried out to the magnetic nanomolecules imprinted polymer of the separation of test one novel nicotine agricultural chemicals piperazine worm pyridine, obtain the XRD figure of the magnetic nanomolecules imprinted polymer of the separation novel nicotine agricultural chemicals piperazine worm pyridine of test one as shown in Figure 3, as can be seen from Figure 3 within the scope of 2 θ=20 ° ~ 80 °, Fe 3o 4siO 2having there are 6 characteristic diffraction peaks in C=C-MIPs, lays respectively at 30.38 °, 35.58 °, 43.14 °, 53.48 °, 57.08 ° and 62.66 °, consistent with the magnetite diffraction peak of the 19-0692 file of the international diffraction central database of JCPDS, corresponding Fe respectively 3o 4(220), (311), (400), (422), (511), (440), maintain Fe 3o 4crystal structure.As can be seen here, coated the failing of to prepare in Molecularly Imprinted Polymer process step by step causes Fe 3o 4the change of crystalline phase.
(4), to the magnetic nanomolecules imprinted polymer of the separation of test one novel nicotine agricultural chemicals piperazine worm pyridine carry out adsorptive capacity detection, process is as follows: the magnetic nanomolecules imprinted polymer (Fe accurately taking the separation novel nicotine agricultural chemicals piperazine worm pyridine of the test one of 40mg 3o 4siO 2and non-molecularly imprinted polymer Fe C=C-MIPs) 3o 4siO 2c=C-NIPs, (being accurate to 0.001g), add piperazine worm pyridine (IPP) acetonitrile solution of the 0.5mmol/L of 20mL respectively, carry out vibration mixing respectively, first leave standstill when vibrating mixing 10min, 20min, 30min, 40min, 60min, 90min, 120min, 150min, 180min, 210min, 240min and adsorb with ndfeb magnet again, get 1mL supernatant liquor, survey the uv-absorbing peak value of supernatant liquor at 350nm place, according to formula (1) calculate in different time to the adsorptive capacity of piperazine worm pyridine (IPP), draw out Fe 3o 4siO 2c=C-MIP and Fe 3o 4siO 2to the adsorptive capacity-time curve of piperazine worm pyridine (IPP) when C=C-NIP changes in time, as shown in Figure 4.
Q = ( C 0 - C t ) V W - - - ( 1 )
Wherein Q is Fe 3o 4siO 2c=C-MIPs and Fe 3o 4siO 2c=C-NIPs adsorbs the amount (mg/g) of piperazine worm pyridine; C 0for adsorbing the concentration (mg/L) of front piperazine worm pyridine (IPP) acetonitrile solution; Ct---the concentration (mg/L) of piperazine worm pyridine (IPP) acetonitrile solution during different time interval; V is the volume (mL) of solution; W is Fe 3o 4siO 2c=C-MIPs and Fe 3o 4siO 2the quality (g) of C=C-NIPs.
Wherein non-molecularly imprinted polymer (Fe 3o 4siO 2do not add piperazine worm pyridine template when C=C-NIPs) preparing, other steps with prepare magnetic nanomolecules imprinted polymer (Fe 3o 4siO 2c=C-MIPs) method is identical.
Magnetic nanomolecules imprinted polymer (the Fe of the separation novel nicotine agricultural chemicals piperazine worm pyridine testing can be drawn in 60min from Fig. 4 3o 4siO 2c=C-MIPs) adsorptive capacity of IPP is increased fast, almost linear with the time, from 60min to 150min, gather way and slow down gradually, after more than 150min, only have the growth of seldom amount.The adsorptive capacity of IPP-MMIPs is adsorbed when 150min and is substantially reached capacity, and when adsorptive capacity is 16.650 ± 0.084mg/g, 240min, maximum saturation adsorptive capacity is 17.305 ± 0.403mg/g.Therefore, adsorption process at least wants 150min to reach adsorption equilibrium.IPP-MNIPs maximum saturation adsorptive capacity is 8.43 ± 0.551mg/g, and the maximum saturation adsorptive capacity of molecular imprinting is 2.0 times of non-molecular imprinting maximum saturation adsorptive capacity, and adsorption efficiency is high.
Wherein the measuring method of piperazine worm pyridine concentration is as follows:
Select ultraviolet spectrophotometry to measure the content of piperazine worm pyridine.
(1) production standard curve: the IPP acetonitrile solution of configuration 0.5mmol/L, measure the IPP acetonitrile solution constant volume of 0.4mL, 0.6mL, 0.8mL, 1.0mL and 1.2mL respectively in 10mL volumetric flask, choose Abs and do qualitative and quantitative analysis at the absorption peak at 350nm place, the uv-absorbing peak value at scanning 350nm place.Using acetonitrile as blank, measure light absorption value operation and average in triplicate, obtain typical curve and regression equation, as shown in Figure 5, regression equation is y=15.98x-0.0042 to graphic representation; Wherein X-coordinate is piperazine worm pyridine content (mmol/L), and ordinate zou is light absorption value (Abs), standard error R 2=0.99995.
(2) samples contg measures: pipette samples liquid 1.0mL is by above-mentioned steps operation, and densitometric absorbance, calculates piperazine worm pyridine content with typical curve.(n＝3)。
(5), to the magnetic nanomolecules imprinted polymer of the separation of test one novel nicotine agricultural chemicals piperazine worm pyridine carry out recycling Efficiency testing, process is as follows:
1. the Fe of 40mg is accurately taken 3o 4siO 2c=C-MIPs, adds the IPP acetonitrile solution of the 0.5mmol/L of 20mL, and after absorption 12h, leave standstill ndfeb magnet absorption, survey supernatant liquor at the uv-absorbing peak value at 350nm place, wash away IPP with elutriant, until detect without IPP, vacuum-drying is for subsequent use; 2. repeating step 1. 5 times.
Its adsorptive capacity of each calculating also draws out repeating utilization factor figure as shown in Figure 6, and as seen from Figure 6, repeat absorption through five times, adsorptive capacity does not have considerable change, Fe 3o 4siO 2the adsorptive capacity of C=C-MIP reduces by 12.45%, but still remains on about 85.3%.
(6), the magnetic nanomolecules imprinted polymer of the separation of test one novel nicotine agricultural chemicals piperazine worm pyridine is carried out to the detection of adsorption selectivity, process is as follows:
Select other four kinds of anabasine pesticide Provados, Diacloden, thiacloprid, Ti304 as competitive molecule together with the pyridine of test one discernible piperazine worm, by evaluating Fe to five kinds of anabasine pesticide adsorptive capacitys 3o 4siO 2the selective recognition ability of C=C-MIP.
Accurately take the Fe of 40mg 3o 4siO 2c=C-MIPs and Fe 3o 4siO 2c=C-NIPs, add the IPP acetonitrile solution of the 0.5mmol/L of 20mL, Provado acetonitrile solution, Diacloden acetonitrile solution, thiacloprid acetonitrile solution, Ti304 acetonitrile solution respectively, after absorption 12h, leave standstill ndfeb magnet absorption, after dilution, survey uv-absorbing peak value at respective wavelength place respectively.In linearity range, utilize ultra-violet and visible spectrophotometer to make typical curve respectively to Provado, Diacloden, thiacloprid, Ti304, uv-absorbing peak value is substituted into typical curve, goes out Fe according to regression equation calculation 3o 4siO 2c=C-MIPs and Fe 3o 4siO 2the adsorptive capacity of C=C-NIPs, makes histogram, as shown in Figure 7.As seen from Figure 7, Fe 3o 4siO 2c=C-MIPs is to the adsorptive capacity of IPP considerably beyond the adsorptive capacity to other kind of anabasine pesticide, and the adsorptive capacity of Ti304 comes second, Provado and Diacloden adsorptive capacity minimum.Fe is described 3o 4siO 2c=C-MIPs has good single-minded recognition capability to IPP.

Claims (10)

1. be separated a preparation method for the magnetic nanomolecules imprinted polymer of nicotine agricultural chemicals piperazine worm pyridine, it is characterized in that the method is carried out according to the following steps:
One, Fe is prepared 3o 4magnetic nano-particle: iron trichloride is dissolved in ethylene glycol, supersound process is to existing without solid, then anhydrous sodium acetate is added, low whipping speed is stir 25min ~ 35min under the condition of 400r/min ~ 600r/min, be transferred in reactor, be react 11h ~ 13h under the condition of 180 ~ 220 DEG C in temperature, stopped reaction, leave standstill 15min ~ 25min, then magneticseparation sedimentation is carried out with ndfeb magnet, after pouring out supernatant liquid, carrying out washing treatment is carried out to the solid matter obtained, then be vacuum-drying 5h ~ 7h under the condition of 40 ~ 50 DEG C in temperature by material after washing, obtain Fe 3o 4magnetic nano-particle, described carrying out washing treatment process is as follows: 1. use the washing with alcohol solid matter of 95%, then carries out magneticseparation sedimentation with ndfeb magnet, obtains solid product after pouring out supernatant liquid, 2. repeating step 1. 3 times, 3. use distilled water washed solid, then carry out magneticseparation sedimentation with ndfeb magnet, after pouring out supernatant liquid, obtain solid product, 4. repeating step 3. 3 times,
The quality of described iron trichloride is 13.5g:(450 ~ 550 with the ratio of the volume of ethylene glycol) mL; Described iron trichloride and the mass ratio of anhydrous sodium acetate are 13.5:(35 ~ 37);
The ethanol of each carrying out washing treatment used 95% and the volume ratio of ethylene glycol are 1:(4.5 ~ 5.5); The volume ratio of each carrying out washing treatment institute's distilled water and ethylene glycol is 1:(4.5 ~ 5.5);
Two, Fe 3o 4the modification of magnetic nano-particle; To the Fe that step one obtains 3o 4add hydrochloric acid and trisodium citrate in magnetic nano-particle, supersound process 15min ~ 25min, be then vacuum-drying 5h ~ 7h under the condition of 40 ~ 50 DEG C in temperature, complete modification, obtain the Fe being with identical charges 3o 4magnetic nano-particle;
The Fe that described step one obtains 3o 4the quality of magnetic nano-particle is 0.4g:(12 ~ 18 with the ratio of the volume of hydrochloric acid) mL; The Fe that described step one obtains 3o 4the quality of magnetic nano-particle is 0.4g:(12 ~ 18 with the ratio of the volume of trisodium citrate) mL;
Three, Fe 3o 4the silanization of magnetic nano-particle: to the Fe of the band identical charges that step 2 obtains 3o 4virahol and distilled water is added in magnetic nano-particle, supersound process is to being uniformly dispersed, then be that 1.8mL/min ~ 2.3mL/min dropwise adds ammoniacal liquor with rate of addition, after dropwising, be that 1.8mL/min ~ 2.3mL/min dropwise adds tetraethoxy again with rate of addition, after dropwising, be that 400r/min ~ 600r/min stirs 10h ~ 14h with stirring velocity under room temperature, then magneticseparation sedimentation is carried out with ndfeb magnet, after pouring out supernatant liquid, carrying out washing treatment is carried out to the solid matter obtained, then be vacuum-drying 5h ~ 7h under the condition of 40 ~ 50 DEG C in temperature by material after washing, complete silylating reagent, obtain Fe 3o 4siO 2particulate, described carrying out washing treatment process is as follows: 1. use the washing with alcohol solid matter of 95%, then carries out magneticseparation sedimentation with ndfeb magnet, obtains solid product after pouring out supernatant liquid, 2. repeating step 1. 3 times, 3. use deionized water wash solid matter, then carry out magneticseparation sedimentation with ndfeb magnet, after pouring out supernatant liquid, obtain solid product, 4. repeating step 3. 3 times,
The Fe of the band identical charges that described step 2 obtains 3o 4the quality of magnetic nano-particle is 0.4g:(80 ~ 120 with the ratio of the volume of Virahol) mL; The Fe of the band identical charges that described step 2 obtains 3o 4the quality of magnetic nano-particle is 0.4g:(7 ~ 9 with the ratio of the volume of distilled water) mL; The Fe of the band identical charges that described step 2 obtains 3o 4the quality of magnetic nano-particle is 0.4g:(4 ~ 6 with the ratio of the volume of ammoniacal liquor) mL; The Fe of the band identical charges that described step 2 obtains 3o 4the quality of magnetic nano-particle is 0.4g:(0.8 ~ 1.2 with the ratio of the volume of tetraethoxy) mL;
The ethanol of each carrying out washing treatment used 95% and the volume ratio of Virahol are 1:(0.8 ~ 1.2); The volume ratio of each carrying out washing treatment deionized water used and Virahol is 1:(0.8 ~ 1.2);
Four, double bond modifies Fe 3o 4siO 2the preparation of particulate: the Fe that step 3 is obtained 3o 4siO 2particulate, 3-(trimethoxysilyl) propyl acrylate, dry toluene and triethylamine mix; supersound process is to mixing; under nitrogen atmosphere protection; be stirring and refluxing 22h ~ 24h in the oil bath of 120 ~ 140 DEG C in temperature; magneticseparation sedimentation is carried out with ndfeb magnet after cooling; after pouring out supernatant liquid; carrying out washing treatment is carried out to the solid matter obtained; then be vacuum-drying 5h ~ 7h under the condition of 40 ~ 50 DEG C in temperature by material after washing; complete double bond graft modification, obtain Fe 3o 4siO 2c=C magnetic Nano microsphere; Described carrying out washing treatment process is as follows: 1. use toluene wash solid matter, then carries out magneticseparation sedimentation with ndfeb magnet, obtains solid product after pouring out supernatant liquid; 2. repeating step 1. 3 times; 3. use washing with alcohol solid matter, then carry out magneticseparation sedimentation with ndfeb magnet, after pouring out supernatant liquid, obtain solid product; 4. repeating step 3. 3 times;
The Fe that described step 3 obtains 3o 4siO 2the ratio of the volume of the quality of particulate and 3-(trimethoxysilyl) propyl acrylate is 0.4g:(3 ~ 5) mL; The Fe that described step 3 obtains 3o 4siO 2the quality of particulate is 0.4g:(90 ~ 110 with the ratio of the volume of dry toluene) mL; The Fe that described step 3 obtains 3o 4siO 2the quality of particulate is 0.4g:(1 ~ 3 with the ratio of the volume of triethylamine) mL;
The volume ratio of each carrying out washing treatment toluene used and dry toluene is 1:(0.8 ~ 1.2); The volume ratio of each carrying out washing treatment ethanol used and dry toluene is 1:(0.8 ~ 1.2);
Five, the preparation of the magnetic nanomolecules imprinted polymer of nicotine agricultural chemicals piperazine worm pyridine is separated: be dissolved in acetonitrile by the methacrylic acid of the pyridine of piperazine worm and 1.0mol/L, left at room temperature 10h ~ 14h, then add the Fe that step 4 obtains 3o 4siO 2c=C magnetic Nano microsphere, ethylene glycol dimethacrylate and Diisopropyl azodicarboxylate, be polyreaction 22h ~ 24h under the condition of 45 ~ 55 DEG C in temperature, leave standstill 15min ~ 25min, then magneticseparation sedimentation is carried out with ndfeb magnet, after pouring out supernatant liquid, with elutriant, wash-out is carried out to solid matter, be eluted to and detect without the pyridine of piperazine worm, namely obtain the magnetic nanomolecules imprinted polymer being separated the pyridine of novel nicotine agricultural chemicals piperazine worm;
The Fe that described step 4 obtains 3o 4siO 2the quality of C=C magnetic Nano microsphere and the mol ratio of piperazine worm pyridine are (35 ~ 45) mg:0.1mmol; The Fe that described step 4 obtains 3o 4siO 2ratio (35 ~ 45) mg:0.4mL of the quality of C=C magnetic Nano microsphere and the volume of the methacrylic acid of 1.0mol/L; The Fe that described step 4 obtains 3o 4siO 2ratio (35 ~ 45) mg:16.6mL of the quality of C=C magnetic Nano microsphere and the volume of acetonitrile; The Fe that described step 4 obtains 3o 4siO 2ratio (35 ~ 45) mg:1mL of the quality of C=C magnetic Nano microsphere and the volume of ethylene glycol dimethacrylate; The Fe that described step 4 obtains 3o 4siO 2ratio (35 ~ 45) mg:2mL of the quality of C=C magnetic Nano microsphere and the volume of Diisopropyl azodicarboxylate; Described elutriant is the mixed solution of methyl alcohol and acetic acid, and in elutriant, the volume ratio of methyl alcohol and acetic acid is 9:1.
2. a kind of preparation method being separated the magnetic nanomolecules imprinted polymer of nicotine agricultural chemicals piperazine worm pyridine according to claim 1, is characterized in that the quality of the iron trichloride described in step one is 13.5g:500mL with the ratio of the volume of ethylene glycol; The mass ratio of the iron trichloride described in step one and anhydrous sodium acetate is 13.5:36.
3. a kind of preparation method being separated the magnetic nanomolecules imprinted polymer of nicotine agricultural chemicals piperazine worm pyridine according to claim 1, is characterized in that the Fe that the step one described in step 2 obtains 3o 4the quality of magnetic nano-particle is 0.4g:15mL with the ratio of the volume of hydrochloric acid; The Fe that step one described in step 2 obtains 3o 4the quality of magnetic nano-particle is 0.4g:15mL with the ratio of the volume of trisodium citrate.
4. a kind of preparation method being separated the magnetic nanomolecules imprinted polymer of nicotine agricultural chemicals piperazine worm pyridine according to claim 1, is characterized in that the concentration of the hydrochloric acid described in step 2 is 2mol/L.
5. a kind of preparation method being separated the magnetic nanomolecules imprinted polymer of nicotine agricultural chemicals piperazine worm pyridine according to claim 1, is characterized in that the concentration of the trisodium citrate described in step 2 is 0.5mol/L.
6. a kind of preparation method being separated the magnetic nanomolecules imprinted polymer of nicotine agricultural chemicals piperazine worm pyridine according to claim 1, is characterized in that the Fe of the band identical charges that the step 2 described in step 3 obtains 3o 4the quality of magnetic nano-particle is 0.4g:100mL with the ratio of the volume of Virahol.The Fe of the band identical charges that the step 2 described in step 3 obtains 3o 4the quality of magnetic nano-particle is 0.4g:8mL with the ratio of the volume of distilled water; The Fe of the band identical charges that the step 2 described in step 3 obtains 3o 4the quality of magnetic nano-particle is 0.4g:5mL with the ratio of the volume of ammoniacal liquor; The Fe of the band identical charges that the step 2 described in step 3 obtains 3o 4the quality of magnetic nano-particle is 0.4g:1mL with the ratio of the volume of tetraethoxy.
7. a kind of preparation method being separated the magnetic nanomolecules imprinted polymer of nicotine agricultural chemicals piperazine worm pyridine according to claim 1, is characterized in that the Fe that the step 3 described in step 4 obtains 3o 4siO 2the ratio of the volume of the quality of particulate and 3-(trimethoxysilyl) propyl acrylate is 0.4g:4mL; The Fe that step 3 described in step 4 obtains 3o 4siO 2the quality of particulate is 0.4g:100mL with the ratio of the volume of dry toluene; The Fe that step 3 described in step 4 obtains 3o 4siO 2the quality of particulate is 0.4g:2mL with the ratio of the volume of triethylamine.
8. a kind of preparation method being separated the magnetic nanomolecules imprinted polymer of nicotine agricultural chemicals piperazine worm pyridine according to claim 1, is characterized in that the Fe that the step 4 described in step 5 obtains 3o 4siO 2the quality of C=C magnetic Nano microsphere and the mol ratio of piperazine worm pyridine are 40mg:0.1mmol; The Fe that step 4 described in step 5 obtains 3o 4siO 2the ratio 40mg:0.4mL of the quality of C=C magnetic Nano microsphere and the volume of the methacrylic acid of 1.0mol/L; The Fe that step 4 described in step 5 obtains 3o 4siO 2the ratio 40mg:16.6mL of the quality of C=C magnetic Nano microsphere and the volume of acetonitrile; The Fe that step 4 described in step 5 obtains 3o 4siO 2the ratio 40mg:1mL of the quality of C=C magnetic Nano microsphere and the volume of ethylene glycol dimethacrylate; The Fe that step 4 described in step 5 obtains 3o 4siO 2the ratio 40mg:2mL of the quality of C=C magnetic Nano microsphere and the volume of Diisopropyl azodicarboxylate.
9. a kind of preparation method being separated the magnetic nanomolecules imprinted polymer of nicotine agricultural chemicals piperazine worm pyridine according to claim 1, is characterized in that the concentration of the ethylene glycol dimethacrylate described in step 5 is 1mol/L.
10. a kind of preparation method being separated the magnetic nanomolecules imprinted polymer of nicotine agricultural chemicals piperazine worm pyridine according to claim 1, is characterized in that the concentration of the Diisopropyl azodicarboxylate described in step 5 is 10mg/mL.
CN201510811372.7A 2015-11-20 2015-11-20 A kind of preparation method for the magnetic nanomolecules imprinted polymer for separating nicotine agricultural chemicals paichongding Active CN105254827B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510811372.7A CN105254827B (en) 2015-11-20 2015-11-20 A kind of preparation method for the magnetic nanomolecules imprinted polymer for separating nicotine agricultural chemicals paichongding

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510811372.7A CN105254827B (en) 2015-11-20 2015-11-20 A kind of preparation method for the magnetic nanomolecules imprinted polymer for separating nicotine agricultural chemicals paichongding

Publications (2)

Publication Number Publication Date
CN105254827A true CN105254827A (en) 2016-01-20
CN105254827B CN105254827B (en) 2017-11-03

Family

ID=55094802

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510811372.7A Active CN105254827B (en) 2015-11-20 2015-11-20 A kind of preparation method for the magnetic nanomolecules imprinted polymer for separating nicotine agricultural chemicals paichongding

Country Status (1)

Country Link
CN (1) CN105254827B (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105646805A (en) * 2016-03-26 2016-06-08 吉首大学 Nano TiO2 surface loaded Cu<2+>-nicotine-N-Nitrosodiethylamine composite imprinted material and application
CN105884985A (en) * 2016-05-13 2016-08-24 华南农业大学 Magnetic cadmium ion-imprinted polymer and preparation method thereof
CN106824126A (en) * 2017-01-20 2017-06-13 贵州理工学院 A kind of preparation method of the magnetic mesoporous imprinted material of sandwich structure of energy separating indium
CN106861652A (en) * 2017-01-20 2017-06-20 贵州理工学院 A kind of preparation method of the magnetic mesoporous imprinted material of sandwich structure that can separate gold or silver
CN106861651A (en) * 2017-01-20 2017-06-20 贵州理工学院 A kind of preparation method of the magnetic mesoporous imprinted material of the sandwich structure that can separate samarium, europium, gadolinium, terbium or dysprosium
CN106914227A (en) * 2017-04-12 2017-07-04 中国农业科学院蔬菜花卉研究所 The preparation method and method of evaluating performance of anabasine pesticide fluorescence molecule imprinted polymer microballoon
CN111484629A (en) * 2020-06-11 2020-08-04 中国农业科学院蔬菜花卉研究所 MOFs type molecularly imprinted polymer, preparation method thereof and fluorescent detection method for pesticide residues
CN112375190A (en) * 2020-11-18 2021-02-19 上海理工大学 Method for preparing neonicotinoid pesticide core-shell mesoporous surface molecularly imprinted polymer by one-step method
CN114433034A (en) * 2020-11-02 2022-05-06 中国石油化工股份有限公司 Super-crosslinked polymer modified magnetic nanoparticles and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101053827A (en) * 2007-05-10 2007-10-17 复旦大学 Surface fixing metal ions magnetic microspheres and its preparation method and application
CN102417558A (en) * 2011-11-21 2012-04-18 嘉兴学院 Magnetic molecularly imprinted polymer for separating atrazine, and preparation method for magnetic molecularly imprinted polymer

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101053827A (en) * 2007-05-10 2007-10-17 复旦大学 Surface fixing metal ions magnetic microspheres and its preparation method and application
CN102417558A (en) * 2011-11-21 2012-04-18 嘉兴学院 Magnetic molecularly imprinted polymer for separating atrazine, and preparation method for magnetic molecularly imprinted polymer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
XUAN KONG, ET AL.: "Synthesis and characterization of the core–shell magnetic molecularly imprinted polymers (Fe3O4@MIPs) adsorbents for effective extraction and determination of sulfonamides in the poultry feed", 《JOURNAL OF CHROMATOGRAPHY A》 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105646805A (en) * 2016-03-26 2016-06-08 吉首大学 Nano TiO2 surface loaded Cu<2+>-nicotine-N-Nitrosodiethylamine composite imprinted material and application
CN105646805B (en) * 2016-03-26 2018-01-23 重庆中纳科技有限公司 One kind is carried on nano-TiO2Surface C u2+The compound imprinted material of nicotine diethyl nitrogen nitrosamine and application
CN105884985A (en) * 2016-05-13 2016-08-24 华南农业大学 Magnetic cadmium ion-imprinted polymer and preparation method thereof
CN106861652A (en) * 2017-01-20 2017-06-20 贵州理工学院 A kind of preparation method of the magnetic mesoporous imprinted material of sandwich structure that can separate gold or silver
CN106861651A (en) * 2017-01-20 2017-06-20 贵州理工学院 A kind of preparation method of the magnetic mesoporous imprinted material of the sandwich structure that can separate samarium, europium, gadolinium, terbium or dysprosium
CN106824126A (en) * 2017-01-20 2017-06-13 贵州理工学院 A kind of preparation method of the magnetic mesoporous imprinted material of sandwich structure of energy separating indium
CN106914227A (en) * 2017-04-12 2017-07-04 中国农业科学院蔬菜花卉研究所 The preparation method and method of evaluating performance of anabasine pesticide fluorescence molecule imprinted polymer microballoon
CN106914227B (en) * 2017-04-12 2019-06-11 中国农业科学院蔬菜花卉研究所 The preparation method of anabasine pesticide fluorescent molecule imprinted polymer microballoon
CN111484629A (en) * 2020-06-11 2020-08-04 中国农业科学院蔬菜花卉研究所 MOFs type molecularly imprinted polymer, preparation method thereof and fluorescent detection method for pesticide residues
CN111484629B (en) * 2020-06-11 2022-02-01 中国农业科学院蔬菜花卉研究所 MOFs type molecularly imprinted polymer, preparation method thereof and fluorescent detection method for pesticide residues
CN114433034A (en) * 2020-11-02 2022-05-06 中国石油化工股份有限公司 Super-crosslinked polymer modified magnetic nanoparticles and preparation method and application thereof
CN114433034B (en) * 2020-11-02 2024-05-07 中国石油化工股份有限公司 Super-crosslinked polymer modified magnetic nanoparticle and preparation method and application thereof
CN112375190A (en) * 2020-11-18 2021-02-19 上海理工大学 Method for preparing neonicotinoid pesticide core-shell mesoporous surface molecularly imprinted polymer by one-step method
CN112375190B (en) * 2020-11-18 2022-12-09 上海理工大学 Method for preparing neonicotinoid pesticide core-shell mesoporous surface molecularly imprinted polymer by one-step method

Also Published As

Publication number Publication date
CN105254827B (en) 2017-11-03

Similar Documents

Publication Publication Date Title
CN105254827A (en) Preparation method of magnetic nano molecularly imprinted polymer for separating nicotinic pesticide IPP
CN103497276B (en) A kind of preparation method and application of carbon nanotube-based magnetic organic phosphorous molecule imprinted polymer
CN103570870B (en) Multi-template single dispersing pseudo-ginseng activity saponin(e molecularly imprinted polymer and preparation method thereof
Wu et al. TiO2 nanoparticles-enhanced luminol chemiluminescence and its analytical applications in organophosphate pesticide imprinting
CN104479072A (en) Method for preparing magnetic molecularly-imprinted adsorbent
CN101768238B (en) Citrinin molecular engram material and preparation method as well as application thereof
CN107860759A (en) A kind of preparation method of molecular engram sensor with SERS activity and application
CN103102421A (en) Preparation method of core-shell structure magnetic nano-molecular imprinting polymer for separating starch polysaccharides
CN107118354A (en) A kind of preparation method and application of the compound separating medium of ochratoxin metal organic framework molecular engram
CN105542083B (en) A kind of method for the bi-functional monomer polysaccharide molecule trace nano particle for preparing efficient absorption
CN103497277B (en) Scutellarin molecularly imprinted polymer and its preparation method and application
Zhao et al. One novel chemiluminescence sensor for determination of fenpropathrin based on molecularly imprinted porous hollow microspheres
CN101845127B (en) Method for preparing core-shell structured composite nano surface molecular imprinting polymer of tanshinone compound
CN103265666A (en) Malathion molecularly imprinted polymer and synthetic method of malathion restricted access media-molecularly imprinted polymer
CN106040204B (en) A kind of magnetism micropore organic nanotube hybrid material and its preparation and application
CN108452784A (en) Catecholamine Solid Phase Extraction functional composite material and its preparation method and application
CN107913682A (en) A kind of method for preparing porous temperature sensitive molecular imprinting adsorbing agent
CN106883346B (en) A kind of preparation method of dexamethasone magnetic molecularly imprinted polymer
CN108579696A (en) A kind of theophylline molecular engram material and its preparation method and application of silver nano-grain doping
CN104910339A (en) Magnetic molecular imprinting polyion liquid for detecting ractopamine as well as preparation method and application of magnetic molecular imprinting polyion liquid
CN104693363B (en) Artesunate surface molecule print porous magnetic cellulose microsphere and its preparation method and application
CN105403694B (en) A kind of PS@SiO for detecting paraquat molecule2The preparation method of artificial antibody
Cheng et al. Development of hydroxypropyl cellulose and graphene oxide modified molecularly imprinted polymers for separation and enrichment of podophyllotoxin
Zang et al. A novel high selectivity chemiluminescence sensor for fenvalerate based on double-sided hollow molecularly imprinted materials
CN106589217B (en) A kind of High Internal Phase Emulsion of borate type modification prepares the preparation method of macropore imprinted polymer adsorbent

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant