CN105254827B - A kind of preparation method for the magnetic nanomolecules imprinted polymer for separating nicotine agricultural chemicals paichongding - Google Patents
A kind of preparation method for the magnetic nanomolecules imprinted polymer for separating nicotine agricultural chemicals paichongding Download PDFInfo
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Abstract
A kind of preparation method for the magnetic nanomolecules imprinted polymer for separating nicotine agricultural chemicals paichongding.A kind of preparation method for the magnetic nanomolecules imprinted polymer for separating nicotine agricultural chemicals paichongding.The problem of present invention is in order to solve the method currently without the magnetic nanomolecules imprinted polymer for preparing separable nicotine agricultural chemicals paichongding.Method：First, Fe is prepared3O4Magnetic nano-particle；2nd, Fe3O4The modification of magnetic nano-particle；3rd, Fe3O4The silanization of magnetic nano-particle；4th, double bond modification Fe3O4@SiO2The preparation of particulate；5th, the preparation of the magnetic nanomolecules imprinted polymer of separation nicotine agricultural chemicals paichongding.Product of the present invention is 17.305 ± 0.403mg/g to the maximum saturation adsorbance of paichongding, is 2.0 times of non-molecular engram maximum saturation adsorbance, adsorbance remains at 85.3% or so, high recycling rate after five repetitions are adsorbed.
Description
Technical field
The present invention relates to a kind of preparation method for the molecularly imprinted polymer for separating nicotine agricultural chemicals paichongding.
Background technology
Paichongding (IPP) is the third generation nicotinic insecticide of China's independent research, chemical name be 1- ((6- chloropyridines-
3- yls) methyl) -5- propoxyl group -7- methyl -8- nitros -1,2,3,5,6,7- hexahydro imidazoles [1,2-a] pyridines can be widely used for
The preventing and treating of the various crop insect such as fruit tree, grain, vegetables.It is a large amount of using with food chain into human body poisoning can be caused, therefore
Need badly to extract from food and isolate the progress detection monitoring of paichongding agricultural chemicals.But the crops such as fruit, grain, vegetables matrix is answered
It is miscellaneous, the composition of analysis detection is disturbed rich in protein, carbohydrate, vitamin, pigment etc..Therefore a kind of specific recognition piperazine worm is found
The fast separating process of pyridine is for setting up accurate sensitive paichongding detection method, ensuring that food security is significant.
Magnetic Nano surface molecule print technology provides new approaches for the quick identification separation of paichongding agricultural chemicals.Tradition point
Eluted template molecule after sub- imprinted polymer is polymerize in a solvent by template molecule, function monomer, crosslinking agent and initiator,
There is the rigid polymer with particular space structure hole of template molecule so that " trace " is made.Molecular imprinted polymer on surface is
In carrier surface polymerizable molecular imprinted layer, action site is located at carrier particle surface or close to surface, not only reduce embedding existing
As, and non-specific adsorption is reduced, make binding ability higher, also faster mass transfer rate and Geng Gao recognition efficiencies.To have
It is magnetic, the magnetic nano-particle that good dispersion, specific surface area are big is carrier, nicotine agricultural chemicals paichongding is received for the magnetic of template molecule
Rice molecular imprinted polymer on surface combines advanced magnetic Nano technology and surface molecule print technology, can quickly, accurately
The identification from complicated food substrate isolate paichongding residues of pesticides in food.
At present, the separation method for carrying out nicotine agricultural chemicals paichongding using magnetic nanomolecules trace has no report.
So that a kind of magnetic nanomolecules imprinted polymer for separating paichongding is prepared, so as to quick, accurate, efficient
Paichongding of isolating be necessary.
The content of the invention
Magnetic nanomolecules trace polymerization of the invention in order to solve currently without the separable nicotine agricultural chemicals paichongding of preparation
The problem of method of thing, and a kind of preparation side for the magnetic nanomolecules imprinted polymer for separating nicotine agricultural chemicals paichongding is provided
Method.
The present invention a kind of separation nicotine agricultural chemicals paichongding magnetic nanomolecules imprinted polymer preparation method press with
Lower step is carried out：
First, Fe is prepared3O4Magnetic nano-particle：Ferric trichloride is dissolved in ethylene glycol, it is ultrasonically treated to exist to without solid,
Then anhydrous sodium acetate is added, low whipping speed is stirring 25min~35min under conditions of 400r/min~600r/min, is turned
Move in reactor, 11h~13h is reacted under conditions of temperature is 180~220 DEG C, stop reacting, standing 15min~
25min, then carries out magnetic separation sedimentation with ndfeb magnet, pours out after supernatant liquid, and obtained solid matter is washed
Processing is washed, material is dried in vacuo 5h~7h under conditions of temperature is 40~50 DEG C after then washing, and obtains Fe3O4Magnetic is received
Rice corpuscles；Described carrying out washing treatment process is as follows：1. with 95% ethanol washed solid, then carried out with ndfeb magnet
Magnetic separation is settled, and pours out and solid product is obtained after supernatant liquid；2. repeat step 1. 3 times；3. solids is washed with distilled water
Matter, then carries out magnetic separation sedimentation with ndfeb magnet, pours out and solid product is obtained after supernatant liquid；4. repeat step 3. 3
It is secondary；
The ratio of the quality of described ferric trichloride and the volume of ethylene glycol is 13.5g：(450~550) mL；Described trichlorine
The mass ratio for changing iron and anhydrous sodium acetate is 13.5：(35~37)；
95% ethanol and the volume ratio of ethylene glycol are 1 used in each carrying out washing treatment：(4.5~5.5)；Each carrying out washing treatment
The volume ratio of institute's distilled water and ethylene glycol is 1：(4.5~5.5)；
2nd, Fe3O4The modification of magnetic nano-particle；The Fe obtained to step one3O4In magnetic nano-particle add hydrochloric acid and
Then trisodium citrate, ultrasonically treated 15min~25min is dried in vacuo 5h~7h under conditions of temperature is 40~50 DEG C, complete
Into modification, the Fe with identical charges is obtained3O4Magnetic nano-particle；
The Fe that described step one is obtained3O4The ratio of the quality of magnetic nano-particle and the volume of hydrochloric acid is 0.4g：(12~
18)mL；The Fe that described step one is obtained3O4The ratio of the quality of magnetic nano-particle and the volume of trisodium citrate is 0.4g：
(12~18) mL；
3rd, Fe3O4The silanization of magnetic nano-particle：The Fe with identical charges obtained to step 23O4Magnetic nano particle
Isopropanol and distilled water are added in son, it is ultrasonically treated to being uniformly dispersed, then using rate of addition as 1.8mL/min~2.3mL/
Min is added dropwise after ammoniacal liquor, completion of dropping, then positive silicic acid second is added dropwise by 1.8mL/min~2.3mL/min of rate of addition
After ester, completion of dropping, 10h~14h is stirred by 400r/min~600r/min of mixing speed at room temperature, neodymium iron boron is then used
Magnet carries out magnetic separation sedimentation, pours out after supernatant liquid, and carrying out washing treatment is carried out to obtained solid matter, after then washing
Material is dried in vacuo 5h~7h under conditions of temperature is 40~50 DEG C, completes silylating reagent, obtains Fe3O4@SiO2Particulate；
Described carrying out washing treatment process is as follows：1. with 95% ethanol washed solid, magnetic force point is then carried out with ndfeb magnet
From sedimentation, pour out and solid product is obtained after supernatant liquid；2. repeat step 1. 3 times；3. solid matter is washed with deionized, so
Magnetic separation sedimentation is carried out with ndfeb magnet afterwards, pours out and solid product is obtained after supernatant liquid；4. repeat step 3. 3 times；
The Fe with identical charges that described step two is obtained3O4The quality of magnetic nano-particle and the volume of isopropanol
Than for 0.4g：(80~120) mL；The Fe with identical charges that described step two is obtained3O4The quality of magnetic nano-particle with it is double
The ratio for steaming the volume of water is 0.4g：(7~9) mL；The Fe with identical charges that described step two is obtained3O4Magnetic nano-particle
Quality and ammoniacal liquor volume ratio be 0.4g：(4~6) mL；The Fe with identical charges that described step two is obtained3O4Magnetic
The ratio of the quality of nano-particle and the volume of tetraethyl orthosilicate is 0.4g：(0.8~1.2) mL；
95% ethanol and the volume ratio of isopropanol are 1 used in each carrying out washing treatment：(0.8~1.2)；Each carrying out washing treatment
Deionized water used and the volume ratio of isopropanol are 1：(0.8~1.2)；
4th, double bond modification Fe3O4@SiO2The preparation of particulate：The Fe that step 3 is obtained3O4@SiO2Particulate, 3- (trimethoxies
Base silicyl) propyl acrylate, dry toluene and triethylamine mixing, it is ultrasonically treated to well mixed, protected in nitrogen atmosphere
Under shield, 22h~24h is stirred at reflux in temperature is 120~140 DEG C of oil bath, magnetic force point is carried out after cooling with ndfeb magnet
From sedimentation, pour out after supernatant liquid, carrying out washing treatment is carried out to obtained solid matter, material is 40 in temperature after then washing
5h~7h is dried in vacuo under conditions of~50 DEG C, double bond graft modification is completed, obtains Fe3O4@SiO2@C=C magnetic Nano microspheres；
Described carrying out washing treatment process is as follows：1. toluene washed solid is used, then magnetic separation sedimentation is carried out with ndfeb magnet,
Pour out and solid product is obtained after supernatant liquid；2. repeat step 1. 3 times；3. ethanol washed solid is used, neodymium iron boron is then used
Magnet carries out magnetic separation sedimentation, pours out and solid product is obtained after supernatant liquid；4. repeat step 3. 3 times；
The Fe that described step three is obtained3O4@SiO2The quality of particulate and 3- (trimethoxysilyl) propylacrylate
The ratio of the volume of ester is 0.4g：(3~5) mL；The Fe that described step three is obtained3O4@SiO2The quality of particulate and dry toluene
The ratio of volume is 0.4g：(90~110) mL；The Fe that described step three is obtained3O4@SiO2The quality of particulate and the body of triethylamine
Long-pending ratio is 0.4g：(1~3) mL；
The volume ratio of toluene and dry toluene is 1 used in each carrying out washing treatment：(0.8~1.2)；Used in each carrying out washing treatment
The volume ratio of ethanol and dry toluene is 1：(0.8~1.2)；
5th, the preparation of the magnetic nanomolecules imprinted polymer of separation nicotine agricultural chemicals paichongding：By paichongding and 1.0mol/
L methacrylic acid is dissolved in acetonitrile, and 10h~14h is stood at room temperature, then adds the Fe that step 4 is obtained3O4@SiO2@C=C
Magnetic Nano microsphere, ethylene glycol dimethacrylate and azodiisobutyronitrile, polymerize under conditions of temperature is 45~55 DEG C
22h~24h is reacted, 15min~25min is stood, then carries out magnetic separation sedimentation with ndfeb magnet, pour out supernatant liquid
Afterwards, solid matter is eluted with eluent, is eluted to no paichongding detection, that is, obtains separating the magnetic of nicotine agricultural chemicals paichongding
Property nanometer molecular imprinting polymer；
The Fe that described step four is obtained3O4@SiO2The quality of@C=C magnetic Nano microspheres and the mol ratio of paichongding are
(35~45) mg：0.1mmol；The Fe that described step four is obtained3O4@SiO2The quality of@C=C magnetic Nano microspheres with
Ratio (35~45) mg of the volume of 1.0mol/L methacrylic acid：0.4mL；The Fe that described step four is obtained3O4@SiO2@C
Ratio (35~45) mg of the quality of=C magnetic Nano microspheres and the volume of acetonitrile：16.6mL；What described step four was obtained
Fe3O4@SiO2Ratio (35~45) mg of the quality of@C=C magnetic Nano microspheres and the volume of ethylene glycol dimethacrylate：
1mL；The Fe that described step four is obtained3O4@SiO2The quality of@C=C magnetic Nano microspheres and the volume of azodiisobutyronitrile
Than (35~45) mg：2mL；Described eluent is the mixed liquor of methanol and acetic acid, and in eluent methanol and acetic acid volume
Than for 9:1.
The method that magnetic molecularly imprinted technology separates nicotine agricultural chemicals paichongding is prepared the invention discloses a kind of, first to Fe3O4
Silanization is carried out, then with Fe of 3- (trimethoxysilyl) propyl acrylates to synthesis3O4@SiO2It is modified generation
The Fe of double bond grafting3O4@SiO2@C=C, then with paichongding (IPP) be template, azodiisobutyronitrile (AIBN) be initiator,
Methacrylic acid (MAA) is that function monomer, ethylene glycol dimethacrylate (EGDMA) are crosslinking agent, with Fe3O4@SiO2@C=
C is that paichongding magnetic nanomolecules imprinted polymer is made in carrier.It compensate for that currently without a kind of point of paichongding can be separated
The cavity of sub- imprinted polymer, the magnetic nanomolecules imprinted polymer of obtained separation nicotine agricultural chemicals paichongding is to paichongding
Maximum saturation adsorbance is 17.305 ± 0.403mg/g, is 2.0 times of non-molecular engram maximum saturation adsorbance, adsorption efficiency
Height, is adsorbed, adsorbance does not have significant change, Fe by five repetitions3O4@SiO2@C=C-MIP adsorbance reduction by 12.45%,
But 85.3% or so is remained at, high recycling rate can be applied to separation paichongding field.
Brief description of the drawings
Fig. 1 shines for the ESEM of the magnetic nanomolecules imprinted polymer of the separation nicotine agricultural chemicals paichongding of experiment one
Piece；
Fig. 2 composes for the infrared spectrum of the magnetic nanomolecules imprinted polymer of the separation nicotine agricultural chemicals paichongding of experiment one
Figure；
Fig. 3 is the XRD of the magnetic nanomolecules imprinted polymer of the separation nicotine agricultural chemicals paichongding of experiment one；
Fig. 4 is absorption of the magnetic nanomolecules imprinted polymer of the separation nicotine agricultural chemicals paichongding of experiment one to paichongding
Amount-time plot；Wherein a is Fe3O4@SiO2@C=C-MIPs, b are Fe3O4@SiO2@C=C-NIPs；
Fig. 5 is the canonical plotting for determining paichongding absorbance；
Fig. 6 is the recycling rate of waterused post of the magnetic nanomolecules imprinted polymer of the separation nicotine agricultural chemicals paichongding of experiment one
Shape figure；
Fig. 7 selects recognition capability post for the magnetic nanomolecules imprinted polymer of the separation nicotine agricultural chemicals paichongding of experiment one
Shape figure；WhereinFor Fe3O4@SiO2@C=C-MIPs,For Fe3O4@SiO2@C=C-NIPs.
Embodiment
Technical scheme is not limited to any between detailed description below, in addition to each embodiment
Combination.
Embodiment one：A kind of magnetic nanomolecules trace of separation nicotine agricultural chemicals paichongding of present embodiment gathers
The preparation method of compound is carried out according to the following steps：
First, Fe is prepared3O4Magnetic nano-particle：Ferric trichloride is dissolved in ethylene glycol, it is ultrasonically treated to exist to without solid,
Then anhydrous sodium acetate is added, low whipping speed is stirring 25min~35min under conditions of 400r/min~600r/min, is turned
Move in reactor, 11h~13h is reacted under conditions of temperature is 180~220 DEG C, stop reacting, standing 15min~
25min, then carries out magnetic separation sedimentation with ndfeb magnet, pours out after supernatant liquid, and obtained solid matter is washed
Processing is washed, material is dried in vacuo 5h~7h under conditions of temperature is 40~50 DEG C after then washing, and obtains Fe3O4Magnetic is received
Rice corpuscles；Described carrying out washing treatment process is as follows：1. with 95% ethanol washed solid, then carried out with ndfeb magnet
Magnetic separation is settled, and pours out and solid product is obtained after supernatant liquid；2. repeat step 1. 3 times；3. solids is washed with distilled water
Matter, then carries out magnetic separation sedimentation with ndfeb magnet, pours out and solid product is obtained after supernatant liquid；4. repeat step 3. 3
It is secondary；
The ratio of the quality of described ferric trichloride and the volume of ethylene glycol is 13.5g：(450~550) mL；Described trichlorine
The mass ratio for changing iron and anhydrous sodium acetate is 13.5：(35~37)；
95% ethanol and the volume ratio of ethylene glycol are 1 used in each carrying out washing treatment：(4.5~5.5)；Each carrying out washing treatment
The volume ratio of institute's distilled water and ethylene glycol is 1：(4.5~5.5)；
2nd, Fe3O4The modification of magnetic nano-particle；The Fe obtained to step one3O4In magnetic nano-particle add hydrochloric acid and
Then trisodium citrate, ultrasonically treated 15min~25min is dried in vacuo 5h~7h under conditions of temperature is 40~50 DEG C, complete
Into modification, the Fe with identical charges is obtained3O4Magnetic nano-particle；
The Fe that described step one is obtained3O4The ratio of the quality of magnetic nano-particle and the volume of hydrochloric acid is 0.4g：(12~
18)mL；The Fe that described step one is obtained3O4The ratio of the quality of magnetic nano-particle and the volume of trisodium citrate is 0.4g：
(12~18) mL；
3rd, Fe3O4The silanization of magnetic nano-particle：The Fe with identical charges obtained to step 23O4Magnetic nano particle
Isopropanol and distilled water are added in son, it is ultrasonically treated to being uniformly dispersed, then using rate of addition as 1.8mL/min~2.3mL/
Min is added dropwise after ammoniacal liquor, completion of dropping, then positive silicic acid second is added dropwise by 1.8mL/min~2.3mL/min of rate of addition
After ester, completion of dropping, 10h~14h is stirred by 400r/min~600r/min of mixing speed at room temperature, neodymium iron boron is then used
Magnet carries out magnetic separation sedimentation, pours out after supernatant liquid, and carrying out washing treatment is carried out to obtained solid matter, after then washing
Material is dried in vacuo 5h~7h under conditions of temperature is 40~50 DEG C, completes silylating reagent, obtains Fe3O4@SiO2Particulate；
Described carrying out washing treatment process is as follows：1. with 95% ethanol washed solid, magnetic force point is then carried out with ndfeb magnet
From sedimentation, pour out and solid product is obtained after supernatant liquid；2. repeat step 1. 3 times；3. solid matter is washed with deionized, so
Magnetic separation sedimentation is carried out with ndfeb magnet afterwards, pours out and solid product is obtained after supernatant liquid；4. repeat step 3. 3 times；
The Fe with identical charges that described step two is obtained3O4The quality of magnetic nano-particle and the volume of isopropanol
Than for 0.4g：(80~120) mL；The Fe with identical charges that described step two is obtained3O4The quality of magnetic nano-particle with it is double
The ratio for steaming the volume of water is 0.4g：(7~9) mL；The Fe with identical charges that described step two is obtained3O4Magnetic nano-particle
Quality and ammoniacal liquor volume ratio be 0.4g：(4~6) mL；The Fe with identical charges that described step two is obtained3O4Magnetic
The ratio of the quality of nano-particle and the volume of tetraethyl orthosilicate is 0.4g：(0.8~1.2) mL；
95% ethanol and the volume ratio of isopropanol are 1 used in each carrying out washing treatment：(0.8~1.2)；Each carrying out washing treatment
Deionized water used and the volume ratio of isopropanol are 1：(0.8~1.2)；
4th, double bond modification Fe3O4@SiO2The preparation of particulate：The Fe that step 3 is obtained3O4@SiO2Particulate, 3- (trimethoxies
Base silicyl) propyl acrylate, dry toluene and triethylamine mixing, it is ultrasonically treated to well mixed, protected in nitrogen atmosphere
Under shield, 22h~24h is stirred at reflux in temperature is 120~140 DEG C of oil bath, magnetic force point is carried out after cooling with ndfeb magnet
From sedimentation, pour out after supernatant liquid, carrying out washing treatment is carried out to obtained solid matter, material is 40 in temperature after then washing
5h~7h is dried in vacuo under conditions of~50 DEG C, double bond graft modification is completed, obtains Fe3O4@SiO2@C=C magnetic Nano microspheres；
Described carrying out washing treatment process is as follows：1. toluene washed solid is used, then magnetic separation sedimentation is carried out with ndfeb magnet,
Pour out and solid product is obtained after supernatant liquid；2. repeat step 1. 3 times；3. ethanol washed solid is used, neodymium iron boron is then used
Magnet carries out magnetic separation sedimentation, pours out and solid product is obtained after supernatant liquid；4. repeat step 3. 3 times；
The Fe that described step three is obtained3O4@SiO2The quality of particulate and 3- (trimethoxysilyl) propylacrylate
The ratio of the volume of ester is 0.4g：(3~5) mL；The Fe that described step three is obtained3O4@SiO2The quality of particulate and dry toluene
The ratio of volume is 0.4g：(90~110) mL；The Fe that described step three is obtained3O4@SiO2The quality of particulate and the body of triethylamine
Long-pending ratio is 0.4g：(1~3) mL；
The volume ratio of toluene and dry toluene is 1 used in each carrying out washing treatment：(0.8~1.2)；Used in each carrying out washing treatment
The volume ratio of ethanol and dry toluene is 1：(0.8~1.2)；
5th, the preparation of the magnetic nanomolecules imprinted polymer of separation nicotine agricultural chemicals paichongding：By paichongding and 1.0mol/
L methacrylic acid is dissolved in acetonitrile, and 10h~14h is stood at room temperature, then adds the Fe that step 4 is obtained3O4@SiO2@C=C
Magnetic Nano microsphere, ethylene glycol dimethacrylate and azodiisobutyronitrile, polymerize under conditions of temperature is 45~55 DEG C
22h~24h is reacted, 15min~25min is stood, then carries out magnetic separation sedimentation with ndfeb magnet, pour out supernatant liquid
Afterwards, solid matter is eluted with eluent, is eluted to no paichongding detection, that is, obtains separating the magnetic of nicotine agricultural chemicals paichongding
Property nanometer molecular imprinting polymer；
The Fe that described step four is obtained3O4@SiO2The quality of@C=C magnetic Nano microspheres and the mol ratio of paichongding are
(35~45) mg：0.1mmol；The Fe that described step four is obtained3O4@SiO2The quality of@C=C magnetic Nano microspheres with
Ratio (35~45) mg of the volume of 1.0mol/L methacrylic acid：0.4mL；The Fe that described step four is obtained3O4@SiO2@C
Ratio (35~45) mg of the quality of=C magnetic Nano microspheres and the volume of acetonitrile：16.6mL；What described step four was obtained
Fe3O4@SiO2Ratio (35~45) mg of the quality of@C=C magnetic Nano microspheres and the volume of ethylene glycol dimethacrylate：
1mL；The Fe that described step four is obtained3O4@SiO2The quality of@C=C magnetic Nano microspheres and the volume of azodiisobutyronitrile
Than (35~45) mg：2mL；Described eluent is the mixed liquor of methanol and acetic acid, and in eluent methanol and acetic acid volume
Than for 9:1.
Embodiment two：Present embodiment from unlike embodiment one：Trichlorine described in step one
The ratio for changing the quality of iron and the volume of ethylene glycol is 13.5g：500mL；Ferric trichloride and anhydrous sodium acetate described in step one
Mass ratio be 13.5：36.Other steps are identical with embodiment one with parameter.
Embodiment three：Present embodiment from unlike embodiment one or two：Described in step 2
The Fe that step one is obtained3O4The ratio of the quality of magnetic nano-particle and the volume of hydrochloric acid is 0.4g：15mL；Described in step 2
The Fe that step one is obtained3O4The ratio of the quality of magnetic nano-particle and the volume of trisodium citrate is 0.4g：15mL.Other steps
It is identical with parameter with embodiment one or two.
Embodiment four：Unlike one of present embodiment and embodiment one to three：Institute in step 2
The concentration for the hydrochloric acid stated is 2mol/L.Other steps are identical with one of embodiment one to three with parameter.
Embodiment five：Unlike one of present embodiment and embodiment one to four：Institute in step 2
The concentration for the trisodium citrate stated is 0.5mol/L.Other steps are identical with one of embodiment one to four with parameter.
Embodiment six：Unlike one of present embodiment and embodiment one to five：Institute in step 3
The Fe with identical charges that the step of stating two obtains3O4The ratio of the quality of magnetic nano-particle and the volume of isopropanol is 0.4g：
100mL.The Fe with identical charges that the step of described in step 3 two obtains3O4The quality of magnetic nano-particle and distilled water
The ratio of volume is 0.4g：8mL；The Fe with identical charges that the step of described in step 3 two obtains3O4The matter of magnetic nano-particle
The ratio of amount and the volume of ammoniacal liquor is 0.4g：5mL；The Fe with identical charges that the step of described in step 3 two obtains3O4Magnetic is received
The ratio of the quality of rice corpuscles and the volume of ammoniacal liquor is 0.4g：1mL.One of other steps and parameter and embodiment one to five
It is identical.
Embodiment seven：Unlike one of present embodiment and embodiment one to six：Institute in step 4
The Fe that the step of stating three obtains3O4@SiO2The quality of particulate and the volume of 3- (trimethoxysilyl) propyl acrylate
Than for 0.4g：4mL；The Fe that the step of described in step 4 three obtains3O4@SiO2The quality of particulate and the volume of dry toluene
Than for 0.4g：100mL；The Fe that the step of described in step 4 three obtains3O4@SiO2The quality of particulate and the volume of triethylamine
Than for 0.4g：2mL.Other steps are identical with one of embodiment one to six with parameter.
Embodiment eight：Unlike one of one of present embodiment and embodiment one to seven：Step 5
Described in the step of four obtained Fe3O4@SiO2The quality of@C=C magnetic Nano microspheres and the mol ratio of paichongding are 40mg：
0.1mmol；The Fe that the step of described in step 5 four obtains3O4@SiO2The quality and 1.0mol/L of@C=C magnetic Nano microspheres
Methacrylic acid volume ratio 40mg：0.4mL；The Fe that the step of described in step 5 four obtains3O4@SiO2@C=C magnetic
The ratio 40mg of the quality of nanoparticle and the volume of acetonitrile：16.6mL；The Fe that the step of described in step 5 four obtains3O4@
SiO2The ratio 40mg of the quality of@C=C magnetic Nano microspheres and the volume of ethylene glycol dimethacrylate：1mL；In step 5
The Fe that described step four is obtained3O4@SiO2The ratio of the quality of@C=C magnetic Nano microspheres and the volume of azodiisobutyronitrile
40mg：2mL.Other steps are identical with one of embodiment one to seven with parameter.
Embodiment nine：Unlike one of present embodiment and embodiment one to eight：Institute in step 5
The concentration for the ethylene glycol dimethacrylate stated is 1mol/L.One of other steps and parameter and embodiment one to eight
It is identical.
Embodiment ten：Unlike one of present embodiment and embodiment one to nine：Institute in step 5
The concentration for the azodiisobutyronitrile stated is 10mg/mL.Other steps are identical with one of embodiment one to nine with parameter.
With following verification experimental verification beneficial effects of the present invention：
Experiment one, a kind of preparation method for the magnetic nanomolecules imprinted polymer for separating nicotine agricultural chemicals paichongding are by following
Step is carried out：
First, Fe is prepared3O4Magnetic nano-particle：13.5g ferric trichloride is dissolved in 500mL ethylene glycol, it is ultrasonically treated
Exist to without solid, then add 36g anhydrous sodium acetate, low whipping speed turns to stir 30min under conditions of 500r/min
Move in reactor, react 12h under conditions of temperature is 200 DEG C, stop reaction, stand 20min, then use ndfeb magnet
Magnetic separation sedimentation is carried out, is poured out after supernatant liquid, carrying out washing treatment is carried out to obtained solid matter, material after then washing
6h is dried in vacuo under conditions of temperature is 45 DEG C, Fe is obtained3O4Magnetic nano-particle；Described carrying out washing treatment process is as follows：①
With 100mL 95% ethanol washed solid, magnetic separation sedimentation then is carried out with ndfeb magnet, supernatant liquid is poured out
After obtain solid product；2. repeat step 1. 3 times；3. 100mL distilled water washed solid is used, ndfeb magnet is then used
Magnetic separation sedimentation is carried out, pours out and solid product is obtained after supernatant liquid；4. repeat step 3. 3 times；
2nd, Fe3O4The modification of magnetic nano-particle；The Fe obtained to 0.4g steps one3O4Added in magnetic nano-particle
Then 15mL hydrochloric acid and 15mL trisodium citrate, ultrasonically treated 20min be dried in vacuo under conditions of temperature is 45 DEG C
6h, completes to be modified, obtains the Fe with identical charges3O4Magnetic nano-particle；
3rd, Fe3O4The silanization of magnetic nano-particle：The Fe with identical charges obtained to 0.4g step 23O4Magnetic is received
In rice corpuscles add 100mL isopropanol and 8mL distilled water, it is ultrasonically treated to being uniformly dispersed, then using rate of addition as
2mL/min is added dropwise after 5mL ammoniacal liquor, completion of dropping, then 1mL positive silicic acid is added dropwise by 2mL/min of rate of addition
After ethyl ester, completion of dropping, 12h is stirred by 500r/min of mixing speed at room temperature, then magnetic force is carried out with ndfeb magnet
Separation sedimentation, is poured out after supernatant liquid, is carried out carrying out washing treatment to obtained solid matter, is then in temperature by material after washing
6h is dried in vacuo under conditions of 45 DEG C, silylating reagent is completed, obtains Fe3O4@SiO2Particulate；Described carrying out washing treatment process is such as
Under：1. 100mL 95% ethanol washed solid is used, then magnetic separation sedimentation is carried out with ndfeb magnet, pours out
Solid product is obtained after layer liquid；2. repeat step 1. 3 times；3. 100mL deionized water washed solid is used, neodymium is then used
Iron boron magnets carry out magnetic separation sedimentation, pour out and solid product is obtained after supernatant liquid；4. repeat step 3. 3 times；
4th, double bond modification Fe3O4@SiO2Particulate：The Fe that 0.4g step 3 is obtained3O4@SiO23- (the front threes of particulate, 4mL
Epoxide silicyl) propyl acrylate, 100mL dry toluene and 2mL triethylamine mixing, it is ultrasonically treated equal to mixing
It is even, under nitrogen atmosphere protection, 24h is stirred at reflux in temperature is 130 DEG C of oil bath, magnetic is carried out with ndfeb magnet after cooling
Power separation sedimentation, is poured out after supernatant liquid, and carrying out washing treatment is carried out to obtained solid matter, and material is in temperature after then washing
To be dried in vacuo 6h under conditions of 45 DEG C, double bond graft modification is completed, Fe is obtained3O4@SiO2@C=C magnetic Nano microspheres；It is described
Carrying out washing treatment process it is as follows：1. 100mL toluene washed solid is used, magnetic separation is then carried out with ndfeb magnet and is sunk
Drop, pours out and solid product is obtained after supernatant liquid；2. repeat step 1. 3 times；3. 100mL ethanol washed solid is used, so
Magnetic separation sedimentation is carried out with ndfeb magnet afterwards, pours out and solid product is obtained after supernatant liquid；4. repeat step 3. 3 times；
5th, the preparation of the magnetic nanomolecules imprinted polymer of separation nicotine agricultural chemicals paichongding：By 0.1mmol paichongding
It is dissolved in 0.4mL 1.0mol/L methacrylic acid in 16.6mL acetonitrile, 12h is stood at room temperature, then adds 40mg's
The Fe that step 4 is obtained3O4@SiO2The azo two of@C=C magnetic Nano microspheres, 1mL ethylene glycol dimethacrylate and 2mL
Isobutyronitrile, the polymerisation 24h under conditions of temperature is 50 DEG C, stands 20min, then carries out magnetic separation with ndfeb magnet
Sedimentation, pours out after supernatant liquid, solid matter is eluted with eluent, is eluted to no paichongding detection, that is, is separated
The magnetic nanomolecules imprinted polymer of nicotine agricultural chemicals paichongding；
Described eluent is the mixed liquor of methanol and acetic acid, and the volume ratio of methanol and acetic acid is 9 in eluent:1.
(1) Electronic Speculum, is scanned to the magnetic nanomolecules imprinted polymer of the separation nicotine agricultural chemicals paichongding of experiment one
Detection, as a result as shown in figure 1, as seen from Figure 1, testing the magnetic nanomolecules trace of one separation nicotine agricultural chemicals paichongding
Polymer surfaces are coarse rough, and adhesion phenomenon occurs in part magnetic molecularly imprinted polymer microballoon, and in magnetic molecule print
The cavity that the form that mark polymer surfaces occurs in that differs, illustrates being successfully prepared for molecularly imprinted polymer.
(2) infrared spectrum, is carried out to the magnetic nanomolecules imprinted polymer of the separation nicotine agricultural chemicals paichongding of experiment one
Detection, obtain experiment one as shown in Figure 2 separation nicotine agricultural chemicals paichongding magnetic nanomolecules imprinted polymer it is infrared
Spectrum spectrogram, as can be seen from Figure 2 in 582cm-1Place occurs in that Fe-O stretching vibration peak, is Fe3O4Characteristic peak, show
Successfully synthesize Fe3O4Particle.Due to Fe3O4Magnetic particle core is coated on nexine, so its characteristic absorption peaks are weaker.
1091cm-1The absworption peak at place is Si-O-Si stretching vibration peak, 958cm-1Locate the stretching vibration peak for Si-O-H, 800cm-1Place
For Si-O stretching vibration peak, 466cm-1Locate the stretching vibration peak for O-Si-O, these characteristic peaks are all SiO2Principal character
Absworption peak, indicates Fe3O4Silane surface is combined to success.1731cm-1Locate the characteristic absorption peak for ester carbonyl group, be 3- (front threes
Epoxide silicyl) propyl acrylate characteristic peak, show successfully to be grafted double bond.2952cm-1Locate as obvious saturation C-H
Stretching vibration absworption peak, 1456cm-1And 1390cm-1For C-C characteristic absorption peaks, show Fe3O4@SiO2Contain in@C=C-MIP
Ethylene glycol dimethacrylate (EDGMA) cellular construction repeated, illustrates that molecularly imprinted polymer is synthesized successfully.
(3), the magnetic nanomolecules imprinted polymer progress X-ray to the separation nicotine agricultural chemicals paichongding of experiment one is spread out
Firing table is levied, and obtains the XRD of the magnetic nanomolecules imprinted polymer of the separation nicotine agricultural chemicals paichongding of experiment one as shown in Figure 3
Figure, as can be seen from Figure 3 in the range of 2 θ=20 °~80 °, Fe3O4@SiO2@C=C-MIPs occur in that 6 characteristic diffraction peaks,
It is located at 30.38 °, 35.58 °, 43.14 °, 53.48 °, 57.08 ° and 62.66 ° respectively, with the international diffraction central databases of JCPDS
19-0692 files magnetic iron ore diffraction peak it is consistent, Fe is corresponded to respectively3O4(220), (311), (400), (422), (511),
(440) Fe, is maintained3O4Crystal structure.As can be seen here, the cladding during Molecularly Imprinted Polymer step by step is prepared to fail to cause
Fe3O4The change of crystalline phase.
(4) adsorbance inspection, is carried out to the magnetic nanomolecules imprinted polymer of the separation nicotine agricultural chemicals paichongding of experiment one
Survey, process is as follows：The magnetic nanomolecules imprinted polymer of the separation nicotine agricultural chemicals paichongding of the accurate experiment one for weighing 40mg
(Fe3O4@SiO2@C=C-MIPs) and non-molecularly imprinted polymer Fe3O4@SiO2@C=C-NIPs, (being accurate to 0.001g), point
Not Jia Ru 20mL 0.5mmol/L paichongding (IPP) acetonitrile solution, respectively carry out vibration mixing, vibration mixing 10min,
First stand and use again when 20min, 30min, 40min, 60min, 90min, 120min, 150min, 180min, 210min, 240min
Ndfeb magnet is adsorbed, and takes 1mL supernatants, is surveyed UV absorption peak value of the supernatant at 350nm, is counted according to formula (1)
The adsorbance in different time to paichongding (IPP) is calculated, Fe is drawn out3O4@SiO2@C=C-MIP and Fe3O4@SiO2@C=C-
To adsorbance-time graph of paichongding (IPP) when NIP is changed over time, as shown in Figure 4.
Wherein Q is Fe3O4@SiO2@C=C-MIPs and Fe3O4@SiO2@C=C-NIPs adsorb the amount (mg/g) of paichongding；
C0For the concentration (mg/L) of paichongding (IPP) acetonitrile solution before absorption；Ct --- paichongding (IPP) acetonitrile during different time interval
The concentration (mg/L) of solution；V is the volume (mL) of solution；W is Fe3O4@SiO2@C=C-MIPs and Fe3O4@SiO2@C=C-
NIPs quality (g).
Wherein non-molecularly imprinted polymer (Fe3O4@SiO2@C=C-NIPs) when preparing without paichongding template, other
Step is with preparing magnetic nanomolecules imprinted polymer (Fe3O4@SiO2@C=C-MIPs) method it is identical.
The magnetic nanomolecules imprinted polymer of the separation nicotine agricultural chemicals paichongding of experiment one in 60min can be drawn from Fig. 4
(Fe3O4@SiO2@C=C-MIPs) IPP adsorbance is quickly increased, it is almost linear with the time, from 60min to
150min, gathers way and gradually slows down, after more than 150min, only minimal amount of to increase.IPP-MMIPs adsorbance exists
Absorption basically reaches saturation during 150min, and adsorbance is 16.650 ± 0.084mg/g, and maximum saturation adsorbance is during 240min
17.305±0.403mg/g.Therefore, adsorption process at least wants 150min to reach adsorption equilibrium.IPP-MNIPs maximum saturations are inhaled
Attached amount is 8.43 ± 0.551mg/g, and the maximum saturation adsorbance of molecular engram is the 2.0 of non-molecular engram maximum saturation adsorbance
Times, adsorption efficiency is high.
The assay method of wherein paichongding concentration is as follows：
The content of paichongding is determined from ultraviolet spectrophotometry.
(1) standard curve is made：Configure 0.5mmol/L IPP acetonitrile solutions, measure respectively 0.4mL, 0.6mL, 0.8mL,
1.0mL and 1.2mL IPP acetonitrile solutions constant volume chooses absworption peaks of the Abs at 350nm and does qualitative, quantitative in 10mL volumetric flasks
UV absorption peak value at analysis, scanning 350nm.Using acetonitrile as blank control, measurement extinction Value Operations are made even in triplicate
Average, obtains standard curve and regression equation, curve map as shown in figure 5, regression equation is y=15.98x-0.0042；It is wherein horizontal to sit
Paichongding content (mmol/L) is designated as, ordinate is light absorption value (Abs), standard error R2=0.99995.
(2) sample size is determined：Pipette samples liquid 1.0mL is operated by above-mentioned steps, densitometric absorbance, with standard
Curve calculates paichongding content.(n=3).
(5), the magnetic nanomolecules imprinted polymer of the separation nicotine agricultural chemicals paichongding of experiment one is reused
Efficiency testing, process is as follows：
1. 40mg Fe is accurately weighed3O4@SiO2@C=C-MIPs, add 20mL 0.5mmol/L IPP acetonitrile solutions,
Adsorb after 12h, stand ndfeb magnet absorption, survey UV absorption peak value of the supernatant at 350nm, IPP is washed away with eluent,
Untill being detected without IPP, it is dried in vacuo standby；2. repeat step 1. 5 times.
Its adsorbance is calculated every time and recycling rate of waterused figure is drawn out as shown in fig. 6, as seen from Figure 6, by five repetitions
Absorption, adsorbance does not have significant change, Fe3O4@SiO2@C=C-MIP adsorbance reduction by 12.45%, but remain at
85.3% or so.
(6) absorption selection, is carried out to the magnetic nanomolecules imprinted polymer of the separation nicotine agricultural chemicals paichongding of experiment one
The detection of property, process is as follows：
Select what other four kinds of anabasine pesticide imidacloprids, Diacloden, thiacloprid, Nitenpyram can recognize that with experiment one
Paichongding is together as competitive molecule, by evaluating Fe to five kinds of anabasine pesticide adsorbances3O4@SiO2@C=C-MIP
Selection recognition capability.
The accurate Fe for weighing 40mg3O4@SiO2@C=C-MIPs and Fe3O4@SiO2@C=C-NIPs, are separately added into 20mL's
0.5mmol/L IPP acetonitrile solutions, imidacloprid acetonitrile solution, Diacloden acetonitrile solution, thiacloprid acetonitrile solution, Nitenpyram
After acetonitrile solution, absorption 12h, ndfeb magnet absorption is stood, UV absorption peak value is surveyed after dilution at respective wavelength respectively.
Standard is made respectively to imidacloprid, Diacloden, thiacloprid, Nitenpyram using ultra-violet and visible spectrophotometer in the range of linearity
Curve, substitutes into standard curve by UV absorption peak value, Fe is gone out according to regression equation calculation3O4@SiO2@C=C-MIPs and Fe3O4@
SiO2@C=C-NIPs adsorbance, makes block diagram, as shown in Figure 7.As seen from Figure 7, Fe3O4@SiO2@C=C-MIPs
To IPP adsorbance considerably beyond the adsorbance to other kind of anabasine pesticide, the adsorbance of Nitenpyram comes second,
Imidacloprid and Diacloden adsorbance are minimum.Illustrate Fe3O4@SiO2@C=C-MIPs have preferable single-minded recognition capability to IPP.
Claims (10)
1. a kind of preparation method for the magnetic nanomolecules imprinted polymer for separating nicotine agricultural chemicals paichongding, it is characterised in that the party
Method is carried out according to the following steps：
First, Fe is prepared3O4Magnetic nano-particle：Ferric trichloride is dissolved in ethylene glycol, it is ultrasonically treated to exist to without solid, then
Anhydrous sodium acetate is added, low whipping speed is stirring 25min~35min under conditions of 400r/min~600r/min, is transferred to
In reactor, 11h~13h is reacted under conditions of temperature is 180~220 DEG C, stops reaction, 15min~25min is stood, so
Magnetic separation sedimentation is carried out with ndfeb magnet afterwards, is poured out after supernatant liquid, carrying out washing treatment is carried out to obtained solid matter, so
Material is dried in vacuo 5h~7h under conditions of temperature is 40~50 DEG C after washing afterwards, obtains Fe3O4Magnetic nano-particle；Institute
The carrying out washing treatment process stated is as follows：1. with 95% ethanol washed solid, then carry out magnetic separation with ndfeb magnet
Sedimentation, pours out and solid product is obtained after supernatant liquid；2. repeat step 1. 3 times；3. distilled water washed solid, Ran Houyong are used
Ndfeb magnet carries out magnetic separation sedimentation, pours out and solid product is obtained after supernatant liquid；4. repeat step 3. 3 times；
The ratio of the quality of described ferric trichloride and the volume of ethylene glycol is 13.5g：(450~550) mL；Described ferric trichloride
Mass ratio with anhydrous sodium acetate is 13.5：(35~37)；
95% ethanol and the volume ratio of ethylene glycol are 1 used in each carrying out washing treatment：(4.5~5.5)；Used in each carrying out washing treatment
The volume ratio of distilled water and ethylene glycol is 1：(4.5~5.5)；
2nd, Fe3O4The modification of magnetic nano-particle；The Fe obtained to step one3O4Hydrochloric acid and lemon are added in magnetic nano-particle
Then sour trisodium, ultrasonically treated 15min~25min is dried in vacuo 5h~7h under conditions of temperature is 40~50 DEG C, completes to change
Property, obtain the Fe with identical charges3O4Magnetic nano-particle；
The Fe that described step one is obtained3O4The ratio of the quality of magnetic nano-particle and the volume of hydrochloric acid is 0.4g：(12~18)
mL；The Fe that described step one is obtained3O4The ratio of the quality of magnetic nano-particle and the volume of trisodium citrate is 0.4g：(12~
18)mL；
3rd, Fe3O4The silanization of magnetic nano-particle：The Fe with identical charges obtained to step 23O4In magnetic nano-particle
Add isopropanol and distilled water, it is ultrasonically treated to being uniformly dispersed, then by 1.8mL/min~2.3mL/min of rate of addition by
It is added dropwise to after ammoniacal liquor, completion of dropping, then tetraethyl orthosilicate is added dropwise by 1.8mL/min~2.3mL/min of rate of addition, drips
Add after finishing, stir 10h~14h by 400r/min~600r/min of mixing speed at room temperature, then use ndfeb magnet
Magnetic separation sedimentation is carried out, is poured out after supernatant liquid, carrying out washing treatment is carried out to obtained solid matter, material after then washing
5h~7h is dried in vacuo under conditions of temperature is 40~50 DEG C, silylating reagent is completed, obtains Fe3O4@SiO2Particulate；It is described
Carrying out washing treatment process it is as follows：1. with 95% ethanol washed solid, then carried out with ndfeb magnet magnetic separation sink
Drop, pours out and solid product is obtained after supernatant liquid；2. repeat step 1. 3 times；3. solid matter, Ran Houyong is washed with deionized
Ndfeb magnet carries out magnetic separation sedimentation, pours out and solid product is obtained after supernatant liquid；4. repeat step 3. 3 times；
The Fe with identical charges that described step two is obtained3O4The ratio of the quality of magnetic nano-particle and the volume of isopropanol is
0.4g：(80~120) mL；The Fe with identical charges that described step two is obtained3O4The quality and distilled water of magnetic nano-particle
Volume ratio be 0.4g：(7~9) mL；The Fe with identical charges that described step two is obtained3O4The matter of magnetic nano-particle
The ratio of amount and the volume of ammoniacal liquor is 0.4g：(4~6) mL；The Fe with identical charges that described step two is obtained3O4Magnetic Nano
The ratio of the quality of particle and the volume of tetraethyl orthosilicate is 0.4g：(0.8~1.2) mL；
95% ethanol and the volume ratio of isopropanol are 1 used in each carrying out washing treatment：(0.8~1.2)；Used in each carrying out washing treatment
Deionized water and the volume ratio of isopropanol are 1：(0.8~1.2)；
4th, double bond modification Fe3O4@SiO2The preparation of particulate：The Fe that step 3 is obtained3O4@SiO2Particulate, 3- (trimethoxy first
Silylation) propyl acrylate, dry toluene and triethylamine mixing, it is ultrasonically treated to well mixed, under nitrogen atmosphere protection,
22h~24h is stirred at reflux in temperature is 120~140 DEG C of oil bath, carrying out magnetic separation with ndfeb magnet after cooling sinks
Drop, is poured out after supernatant liquid, and carrying out washing treatment is carried out to obtained solid matter, and material is 40~50 in temperature after then washing
5h~7h is dried in vacuo under conditions of DEG C, double bond graft modification is completed, obtains Fe3O4@SiO2@C=C magnetic Nano microspheres；It is described
Carrying out washing treatment process it is as follows：1. toluene washed solid is used, then magnetic separation sedimentation is carried out with ndfeb magnet, pours out
Solid product is obtained after supernatant liquid；2. repeat step 1. 3 times；3. ethanol washed solid is used, ndfeb magnet is then used
Magnetic separation sedimentation is carried out, pours out and solid product is obtained after supernatant liquid；4. repeat step 3. 3 times；
The Fe that described step three is obtained3O4@SiO2The quality of particulate and 3- (trimethoxysilyl) propyl acrylate
The ratio of volume is 0.4g：(3~5) mL；The Fe that described step three is obtained3O4@SiO2The quality of particulate and the volume of dry toluene
Ratio be 0.4g：(90~110) mL；The Fe that described step three is obtained3O4@SiO2The quality of particulate and the volume of triethylamine
Than for 0.4g：(1~3) mL；
The volume ratio of toluene and dry toluene is 1 used in each carrying out washing treatment：(0.8~1.2)；Ethanol used in each carrying out washing treatment
Volume ratio with dry toluene is 1：(0.8~1.2)；
5th, the preparation of the magnetic nanomolecules imprinted polymer of separation nicotine agricultural chemicals paichongding：By paichongding and 1.0mol/L
Methacrylic acid is dissolved in acetonitrile, and 10h~14h is stood at room temperature, then adds the Fe that step 4 is obtained3O4@SiO2@C=C magnetic
Property nanoparticle, ethylene glycol dimethacrylate and azodiisobutyronitrile, temperature be polymerize under conditions of 45~55 DEG C it is anti-
22h~24h is answered, 15min~25min is stood, then carries out magnetic separation sedimentation with ndfeb magnet, pour out after supernatant liquid,
Solid matter is eluted with eluent, no paichongding detection is eluted to, that is, obtains separating the magnetic of nicotine agricultural chemicals paichongding
Nanometer molecular imprinting polymer；
The Fe that described step four is obtained3O4@SiO2The quality of@C=C magnetic Nano microspheres and the mol ratio of paichongding are 40mg：
0.1mmol；The Fe that described step four is obtained3O4@SiO2The quality of@C=C magnetic Nano microspheres and 1.0mol/L methyl-prop
The ratio 40mg of the volume of olefin(e) acid：0.4mL；The Fe that described step four is obtained3O4@SiO2The quality of@C=C magnetic Nano microspheres
With ratio (35~45) mg of the volume of acetonitrile：16.6mL；The Fe that described step four is obtained3O4@SiO2@C=C magnetic Nanos are micro-
Ratio (35~45) mg of the quality of ball and the volume of ethylene glycol dimethacrylate：1mL；What described step four was obtained
Fe3O4@SiO2Ratio (35~45) mg of the quality of@C=C magnetic Nano microspheres and the volume of azodiisobutyronitrile：2mL；Described
Eluent is the mixed liquor of methanol and acetic acid, and the volume ratio of methanol and acetic acid is 9 in eluent:1.
2. a kind of preparation of magnetic nanomolecules imprinted polymer for separating nicotine agricultural chemicals paichongding according to claim 1
Method, it is characterised in that the ratio of the quality of the ferric trichloride described in step one and the volume of ethylene glycol is 13.5g：500mL；Step
The mass ratio of ferric trichloride and anhydrous sodium acetate described in rapid one is 13.5：36.
3. a kind of preparation of magnetic nanomolecules imprinted polymer for separating nicotine agricultural chemicals paichongding according to claim 1
Method, it is characterised in that one obtained Fe the step of described in step 23O4The quality of magnetic nano-particle and the volume of hydrochloric acid
Than for 0.4g：15mL；The Fe that the step of described in step 2 one obtains3O4The quality of magnetic nano-particle and trisodium citrate
The ratio of volume is 0.4g：15mL.
4. a kind of preparation of magnetic nanomolecules imprinted polymer for separating nicotine agricultural chemicals paichongding according to claim 1
Method, it is characterised in that the concentration of the hydrochloric acid described in step 2 is 2mol/L.
5. a kind of preparation of magnetic nanomolecules imprinted polymer for separating nicotine agricultural chemicals paichongding according to claim 1
Method, it is characterised in that the concentration of the trisodium citrate described in step 2 is 0.5mol/L.
6. a kind of preparation of magnetic nanomolecules imprinted polymer for separating nicotine agricultural chemicals paichongding according to claim 1
Method, it is characterised in that the two obtained Fe with identical charges the step of described in step 33O4The quality of magnetic nano-particle with
The ratio of the volume of isopropanol is 0.4g：100mL；The Fe with identical charges that the step of described in step 3 two obtains3O4Magnetic is received
The ratio of the quality of rice corpuscles and the volume of distilled water is 0.4g：8mL；The band identical charges that the step of described in step 3 two obtains
Fe3O4The ratio of the quality of magnetic nano-particle and the volume of ammoniacal liquor is 0.4g：5mL；What the step of described in step 3 two, obtained
Fe with identical charges3O4The ratio of the quality of magnetic nano-particle and the volume of tetraethyl orthosilicate is 0.4g：1mL.
7. a kind of preparation of magnetic nanomolecules imprinted polymer for separating nicotine agricultural chemicals paichongding according to claim 1
Method, it is characterised in that three obtained Fe the step of described in step 43O4@SiO2The quality of particulate and 3- (trimethoxy first silicon
Alkyl) propyl acrylate volume ratio be 0.4g：4mL；The Fe that the step of described in step 4 three obtains3O4@SiO2Particulate
Quality and dry toluene volume ratio be 0.4g：100mL；The Fe that the step of described in step 4 three obtains3O4@SiO2It is micro-
The ratio of the quality of grain and the volume of triethylamine is 0.4g：2mL.
8. a kind of preparation of magnetic nanomolecules imprinted polymer for separating nicotine agricultural chemicals paichongding according to claim 1
Method, it is characterised in that four obtained Fe the step of described in step 53O4@SiO2The quality and second of@C=C magnetic Nano microspheres
The ratio 40mg of the volume of nitrile：16.6mL；The Fe that the step of described in step 5 four obtains3O4@SiO2@C=C magnetic Nano microspheres
Quality and ethylene glycol dimethacrylate volume ratio 40mg：1mL；What the step of described in step 5 four, obtained
Fe3O4@SiO2The ratio 40mg of the quality of@C=C magnetic Nano microspheres and the volume of azodiisobutyronitrile：2mL.
9. a kind of preparation of magnetic nanomolecules imprinted polymer for separating nicotine agricultural chemicals paichongding according to claim 1
Method, it is characterised in that the concentration of the ethylene glycol dimethacrylate described in step 5 is 1mol/L.
10. a kind of system of magnetic nanomolecules imprinted polymer for separating nicotine agricultural chemicals paichongding according to claim 1
Preparation Method, it is characterised in that the concentration of the azodiisobutyronitrile described in step 5 is 10mg/mL.
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