CN101757896B - Preparation method of molecularly imprinted polymer on nano-silica gel surfaces of sulfonylurea herbicides - Google Patents
Preparation method of molecularly imprinted polymer on nano-silica gel surfaces of sulfonylurea herbicides Download PDFInfo
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- CN101757896B CN101757896B CN2009102342394A CN200910234239A CN101757896B CN 101757896 B CN101757896 B CN 101757896B CN 2009102342394 A CN2009102342394 A CN 2009102342394A CN 200910234239 A CN200910234239 A CN 200910234239A CN 101757896 B CN101757896 B CN 101757896B
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Abstract
The invention relates to a preparation method of a molecularly imprinted polymer on nano-silica gel surfaces of sulfonylurea herbicides, which comprises the following steps: preparing SiO2 pellets; ultrasonically dispersing the prepared SiO2 pellets into a toluene solution of gamma-methacryloxypropyl trimethoxy silane, and carrying out backflow reaction to obtain modified SiO2 pellets; adding template molecules and functional monomers into a polymerization solvent and fully shaking up to obtain a pre-assembled solution; ultrasonically dispersing the modified SiO2 pellets into the polymerization solvent, and adding cross-linking agent, initiating agent and the pre-assembled solution; mixing, carrying out ice bath ultrasonic treatment, stirring, introducing N2 for removing oxygen, carrying out temperature programming thermal-initiated polymerization under the N2 atmosphere, centrifuging and removing supernatant liquid; and ultrasonically washing precipitates sequentially with a methanol-acetic acid solution and methanol to obtain polymer pellets the template molecules of which are removed. The molecularly imprinted polymer pellets prepared by the invention not only have specific recognition capability for the template molecules and analogs thereof but also have excellent characteristics of enrichment and recovery, thus the molecularly imprinted polymer pellets can be used as dispersed solid phase extraction materials for separating and enriching the sulfonylurea herbicides in environment, food and other complex samples.
Description
Technical field
The present invention relates to a kind of preparation method of surface-modified nano silica gel bead, also relate at sulfonylurea herbicide and carry out surface molecular imprinted method at described nanometer silica gel.
Background technology
The appearance of sulfonylurea herbicide is the sign that herbicide enters the ultra high efficiency epoch, and it makes the consumption of herbicide by former 1-3kga.i./hm
2Become 1-150g a.i./hm
2This class herbicide broad weed-killing spectrum can be prevented and kill off broad leaved weed effectively, and the time range of dispenser is wide, and is low to mammalian toxicity.Because advantages such as the ultra high efficiency of this type of herbicide, low consumption, low toxicity make this class herbicide be widely used, exactly because but the expansion of its use amount and scope, its residual in crops and the murder by poisoning of human health also more and more paid close attention to by people.Therefore, detection and the control to sulfonylurea herbicide seems more urgent and important.
The detection method of this class herbicide has gas chromatography, liquid chromatography and bioassay method etc. at present, and these methods all must be carried out preliminary treatment to sample before measuring, and removes and disturbs impurity, the component of enriched with trace determinand.General pre-treating method has the distribution of liquid liquid, SPE, dispersion SPE, immune column chromatography technology etc. at present.Wherein disperseing solid phase extraction techniques is a kind of extraction, purification, the beneficiation technologies that is similar to SPE, because need not to load into post, simple to operate, can directly handle solid-state, semisolid, thickness sample, the solvent use amount is few, and treatment effeciency is high and develop rapidly.But common dispersion solid phase extraction filler all is nonspecific to the absorption of object, and selectivity is low, is subject to the interference of complex matrices, has influenced pre-treatment efficient.This just requires to develop a kind of separation and purification material that sulfonylurea herbicide is had high selectivity and high-affinity.
In recent years, (Molecularly Imprinted Polymers, MIPs) the develop into high-affinity, the high selectivity separation that solve the residues of pesticides composition provide a potential possibility to molecularly imprinted polymer.Molecular imprinting is based on a kind of functional polymer technology of preparing on the molecular recognition basis, adopt target molecule or analog as template when this polymer is synthetic, after synthetic with the template wash-out, space structure and group have been kept with the template molecule complementation, and has " memory " function, when its once more with target molecule meet can be special combine with target molecule, separate and the effect of enrichment target molecule thereby reach.China Agricultural University (CN 1245422C) discloses a kind of method for preparing the sulfonylureas herbicide molecular imprinted polymer, Zhejiang University (CN101185853A) discloses a kind of preparation method of sulfonylureas herbicide molecular marking superfine fibre film, other has the bibliographical information [J.Bastide of some molecularly imprinted polymers, J.P.Cambon, Anal.Chim.Acta, 542 (2005) 97-103; Qing-Zhi Zhu, Karsten Haupt, Anal.Chim.Acta, 468 (2002) 217-227].But these molecularly imprinted polymers synthetic all is the mode with polymerisation in bulk to be prepared, though the material that makes still has a lot of template molecules to be in material internal through pulverization process, during wash-out, is difficult to remove; When combining with template molecule, template molecule is difficult to again arrive inner binding site, so the affine efficient of polymer is not very desirable.
Summary of the invention
Goal of the invention: at the deficiency of above-mentioned technology, the invention provides a kind of preparation method of nanometer silica gel bead of surface modification, and prepare the ultra-thin High Density Molecular imprinted polymer of sulfonylurea herbicide nano silica gel surface bead with this.Prepared nanometer silica gel bead particle diameter is controlled, and is positioned at its surperficial imprint layer and is evenly distributed, thereby has improved the affine efficient and the stability of this molecularly imprinted polymer greatly.This polymer can further be developed as and disperse the SPE material, realizes the efficient of sulfonylurea herbicide separated and enrichment fast.
Technical scheme: a kind of preparation method of modified Nano silica gel surface molecular imprinted polymer comprises SiO
2The preparation of bead: with the absolute ethyl alcohol is solvent, and concentrated ammonia liquor is a catalyst, and positive tetraethyl orthosilicate (TEOS) is silicon source synthesis of nano SiO
2Bead, supersound washing is extremely neutral, centrifugal repeatedly with absolute ethyl alcohol, is dried to constant weight, and standby, preparation process is:
(1) with the SiO that makes
2Bead is ultrasonic be dispersed in 10% (v/v) γ-methacryloxypropyl trimethoxy silane (in the toluene solution of γ-MPTS), logical N
2Deoxygenation is stirred, and 100～120 ℃ are reacted 12～24h down, centrifugal, obtains the SiO of surface modification
2Bead by the methyl alcohol supersound washing, is removed unreacted γ-MPTS, and is centrifugal, is dried to constant weight, standby;
(2) template molecule, function monomer are added in the polymer solvent, fully shake up and make pre-assembling solution;
(3) the modification SiO that step (1) is made
2Bead is ultrasonic to be scattered in the polymer solvent, adds the pre-assembling solution that crosslinking agent, initator and step (2) make, and gained mixed liquor ice-bath ultrasonic stirs, logical N
2Deoxygenation is at N
2Temperature control adds thermal-initiated polymerization under the atmosphere;
(4) the centrifugal supernatant of removing after the polymerisation is used methyl alcohol-acetic acid solution, methyl alcohol supersound washing successively, detects less than template molecule through ultraviolet until supernatant, and methyl alcohol in described methyl alcohol-acetic acid solution: the volume ratio of acetate is 9: 1;
(5) polymer globules that will remove template molecule is dried to constant weight, obtains the molecularly imprinted polymer bead.
Described SiO
2The preparation method of bead is: absolute ethyl alcohol and concentrated ammonia liquor are mixed according to volume ratio at 50: 9, get solution A; Again absolute ethyl alcohol and TEOS are mixed according to volume ratio at 6: 1, get solution B; Under the room temperature solution B is added in the solution A that stirs with 10～15 droplets/second speed Continuous Titration, when the volume ratio of solution A and solution B reached 59: 35, titration finished, and continued to stir 24h; Supersound washing is to neutral, centrifugal repeatedly with absolute ethyl alcohol, and 60 ℃ of following vacuum drying are to constant weight.
In the described step (1), nanometer SiO
2The mass ratio of bead, γ-MPTS 1: 10～1: 30.
In the described step (2), template molecule is metsulfuron-methyl (MSM), and function monomer is methacrylic acid (MAA), and polymer solvent is an acetonitrile, and volume ratio is toluene-acetonitrile mixed liquor or chloroform of 4: 1; The mol ratio of template molecule and function monomer is 1: 2～1: 5.
In the described step (3), crosslinking agent is ethylene glycol dimethacrylate (EGDMA), trimethylol-propane trimethacrylate (TRIM) or divinylbenzene (DVB); Initator be azodiisobutyronitrile (AIBN), benzoyl peroxide (BPO) or 4,4 '-azo two (4-cyanopentanoic acid) (ACVA), initiator amount is 1% of function monomer and the two key gross masses of crosslinking agent.
In the described step (3), modification SiO
2The consumption of bead is the corresponding 0.625mmol template molecule of 0.1g bead, corresponding 50mL polymer solvent.
In the described step (3), template molecule and crosslinking agent mol ratio are 1: 4～1: 16.
In the described step (3), temperature control adds thermal-initiated polymerization, and heating schedule is as follows: 50 ℃ of reaction 6h, be warming up to 60 ℃ of reaction 24h, and be heated to 75 ℃ of reaction 6h again.
Non-imprinted polymer (SiO
2MSM-NIP) preparation process, except that in building-up process, not adding template molecule, all the other steps and SiO
2MSM-MIP is identical.
Beneficial effect: the present invention is in alkaline alcohol solution, and (TEOS) is the silicon source with positive tetraethyl orthosilicate, has prepared mono-dispersed nano silica gel bead, and makes the silica gel functionalization with the silylating reagent of the two keys of band; The nanometer silica gel bead of surface modification with template molecule sulfonylurea herbicide, function monomer and crosslinking agent polymerisation, makes the ultra-thin High Density Molecular imprinted polymer of nano silica gel surface under the initator effect.Adsorption experiment is the result prove, this polymer has the high selectivity adsorption effect to sulfonylurea herbicide, can be used as to disperse the SPE material, and be achieved efficient the separation with enrichment fast of sulfonylurea herbicide.
Silica gel is the inorganic material of a kind of high-crosslinking-degree, high degree of rigidity and high stability, all can keep binding site and in conjunction with the stability in space under environmental conditions such as all kinds of solvents condition and high temperature; Preparation of silica gel is convenient, is easy to chemical modification and design, and the silica gel after the functionalization can be used as the molecularly imprinted polymer carrier, makes recognition site be positioned at the silica gel structure surface, and the combination again of the removal of template molecule and target molecule will become very easy; The silica gel of Nano grade has high specific area in addition, can increase recognition site, thereby improves the efficient of molecular imprinting widely.
The present invention adopts the Continuous Titration method, is solvent with the absolute ethyl alcohol, and concentrated ammonia liquor is a catalyst, and TEOS is the silicon source, has synthesized the SiO of particle diameter at 300～400nm
2Bead, particle diameter is even, good dispersion.The silylating reagent that adopts the two keys of band is to SiO
2Bead carries out surface modification, the modification SiO of gained
2Bead can be further and two key copolymerization of crosslinking agent, function monomer, and temperature programming has prepared the molecularly imprinted polymer bead, has realized SiO
2Imprint surface layer thickness controlled, all even stable, thus recognition speed accelerated, improve marking efficient, help that sulfonylurea herbicide is efficient to be separated and enrichment fast.
Description of drawings
Fig. 1 is the SiO that the present invention makes
2Bead, modification SiO
2The infrared spectrogram of bead and γ-MPTS, wherein (A) SiO
2Bead; (B) modification SiO
2Bead; (C) γ-MPTS.
Fig. 2 is transmission electron microscope (TEM) figure of the molecularly imprinted polymer bead that makes of the present invention.
Fig. 3 is that the present invention makes optimal conditions SiO
2MSM-MIP and SiO
2The static adsorption isothermal curve figure of MSM-NIP.
Fig. 4 is the dynamic adsorption curve figure that the present invention makes optimal conditions molecularly imprinted polymer bead.
Fig. 5 is the molecular structure of sulfonylurea pesticide and chlopyrifos, and the present invention makes the selective absorption figure of optimal conditions molecularly imprinted polymer bead.
The specific embodiment
Below present embodiment is elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, is example with the metsulfuron-methyl, the present invention is described in detail, but do not limit protection scope of the present invention with this.
For making marking site be fixed in the silica gel surface, must carry out modification to the silica gel surface, make it have two keys that copolymerization can take place.This patent has carried out modification with the silane coupler γ-MPTS of the two keys of band to silica gel, and Fig. 2 has shown SiO
2Bead, modification SiO
2The infrared figure of bead and γ-MPTS.At modification SiO
21719cm has appearred on the infrared figure of bead
-1Carbonyl peak, and 2800～3000cm
-1The hydrocarbon stretching vibration peak of methyl, methylene, visible silica gel modification success.
Fig. 3 has shown the TEM figure of molecularly imprinted polymer, and microspherulite diameter is even, and core-shell structure is obvious, wherein SiO
2About inner core 300nm, the about 20nm of polymer layer thickness has realized imprint surface.
With 50mL absolute ethyl alcohol, 9mL concentrated ammonia liquor mix solution A, the high speed magnetic agitation; Again 30mL absolute ethyl alcohol and 5mL TEOS are mixed solution B; Under the room temperature solution B Continuous Titration (10～15 droplets/second) is added in the solution A of high speed magnetic agitation the titration afterreaction 24h that finishes; Supersound washing is to neutral, centrifugal repeatedly with absolute ethyl alcohol, and 60 ℃ of following vacuum drying are to constant weight.
(1) with 0.2g SiO
2Bead is ultrasonic to be scattered in the 40mL toluene solution, adds 2mL γ-MPTS, logical N
2Deoxygenation, magnetic agitation 300rpm, 100 ℃ are reacted 12h down, and methyl alcohol supersound washing repeatedly is centrifugal, removes unreacted γ-MPTS, and 60 ℃ of following vacuum drying are to constant weight;
(2) with mixing in 0.625mmol MSM, the 2.5mmol MAA adding 25mL acetonitrile, fully shake up, place 4h, make pre-assembling solution;
(3) with 0.1g modification SiO
2Bead is ultrasonic to be scattered in the 25mL acetonitrile, adds the pre-assembling solution that 5mmolEGDMA, 0.125mmol AIBN and step (2) make, ice-bath ultrasonic 5min, logical N under the magnetic agitation
2Deoxygenation, temperature control adds thermal-initiated polymerization, and heating schedule is as follows: 50 ℃ of reaction 6h, be warming up to 60 ℃ of reaction 24h, be heated to 75 ℃ of reaction 6h again;
(5) reaction finishes the centrifugal supernatant of removing in back, use successively methyl alcohol-acetate (9: 1, v/v) solution, methyl alcohol supersound washing repeatedly detects less than template molecule through ultraviolet until supernatant;
(6) polymer globules that will remove template molecule places in the vacuum drying chamber, is dried to constant weight under 60 ℃, obtains the molecularly imprinted polymer bead.
Present embodiment template molecule and function monomer ratio are best proportion.
(1) with 0.2g SiO
2Bead is ultrasonic to be scattered in the 40mL toluene solution, adds 2mL γ-MPTS, logical N
2Deoxygenation, magnetic agitation 300rpm, 120 ℃ are reacted 12h down, and methyl alcohol supersound washing repeatedly is centrifugal, removes unreacted γ-MPTS, and 60 ℃ of following vacuum drying are to constant weight;
(2) with mixing in 0.625mmol MSM, the 2.5mmol MAA adding 25mL acetonitrile, fully shake up, place 4h, make pre-assembling solution;
(3) with 0.1g modification SiO
2Bead is ultrasonic to be scattered in the 25mL acetonitrile, adds the pre-assembling solution that 5mmolEGDMA, 0.125mmol AIBN and step (2) make, ice-bath ultrasonic 5min, logical N under the magnetic agitation
2Deoxygenation, temperature control adds thermal-initiated polymerization, and heating schedule is as follows: 50 ℃ of reaction 6h, be warming up to 60 ℃ of reaction 24h, be heated to 75 ℃ of reaction 6h again;
(5) reaction finishes the centrifugal supernatant of removing in back, use successively methyl alcohol-acetate (9: 1, v/v) solution, methyl alcohol supersound washing repeatedly detects less than template molecule through ultraviolet until supernatant;
(6) polymer globules that will remove template molecule places in the vacuum drying chamber, is dried to constant weight under 60 ℃, obtains the molecularly imprinted polymer bead.
(1) with 0.2g SiO
2Bead is ultrasonic to be scattered in the 40mL toluene solution, adds 2mL γ-MPTS, logical N
2Deoxygenation, magnetic agitation 300rpm, 120 ℃ are reacted 24h down, and methyl alcohol supersound washing repeatedly is centrifugal, removes unreacted γ-MPTS, and 60 ℃ of following vacuum drying are to constant weight;
(2) with mixing in 0.625mmol MSM, the 2.5mmol MAA adding 25mL acetonitrile, fully shake up, place 4h, make pre-assembling solution;
(3) with 0.1g modification SiO
2Bead is ultrasonic to be scattered in the 25mL acetonitrile, adds the pre-assembling solution that 5mmolEGDMA, 0.125mmol AIBN and step (2) make, ice-bath ultrasonic 5min, logical N under the magnetic agitation
2Deoxygenation, temperature control adds thermal-initiated polymerization, and heating schedule is as follows: 50 ℃ of reaction 6h, be warming up to 60 ℃ of reaction 24h, be heated to 75 ℃ of reaction 6h again;
(5) reaction finishes the centrifugal supernatant of removing in back, use successively methyl alcohol-acetate (9: 1, v/v) solution, methyl alcohol supersound washing repeatedly detects less than template molecule through ultraviolet until supernatant;
(6) polymer globules that will remove template molecule places in the vacuum drying chamber, is dried to constant weight under 60 ℃, obtains the molecularly imprinted polymer bead.
(1) with 0.2g SiO
2Bead is ultrasonic to be scattered in the 40mL toluene solution, adds 4mL γ-MPTS, logical N
2Deoxygenation, magnetic agitation 300rpm, 120 ℃ are reacted 12h down, and methyl alcohol supersound washing repeatedly is centrifugal, removes unreacted γ-MPTS, and 60 ℃ of following vacuum drying are to constant weight;
(2) with mixing in 0.625mmol MSM, the 2.5mmol MAA adding 25mL acetonitrile, fully shake up, place 4h, make pre-assembling solution;
(3) with 0.1g modification SiO
2Bead is ultrasonic to be scattered in the 25mL acetonitrile, adds the pre-assembling solution that 5mmolEGDMA, 0.125mmol AIBN and step (2) make, ice-bath ultrasonic 5min, logical N under the magnetic agitation
2Deoxygenation, temperature control adds thermal-initiated polymerization, and heating schedule is as follows: 50 ℃ of reaction 6h, be warming up to 60 ℃ of reaction 24h, be heated to 75 ℃ of reaction 6h again;
(5) reaction finishes the centrifugal supernatant of removing in back, use successively methyl alcohol-acetate (9: 1, v/v) solution, methyl alcohol supersound washing repeatedly detects less than template molecule through ultraviolet until supernatant;
(6) polymer globules that will remove template molecule places in the vacuum drying chamber, is dried to constant weight under 60 ℃, obtains the molecularly imprinted polymer bead.
Present embodiment is SiO
2Bead modification optimal conditions.
Embodiment 6. preparation metsulfuron-methyl molecularly imprinted polymer on nano-silica gel surfaces SiO
2MSM-MIP 5
(1) with 0.2g SiO
2Bead is ultrasonic to be scattered in the 40mL toluene solution, adds 6mL γ-MPTS, logical N
2Deoxygenation, magnetic agitation 300rpm, 120 ℃ are reacted 12h down, and methyl alcohol supersound washing repeatedly is centrifugal, removes unreacted γ-MPTS, and 60 ℃ of following vacuum drying are to constant weight;
(2) with mixing in 0.625mmol MSM, the 2.5mmol MAA adding 25mL acetonitrile, fully shake up, place 4h, make pre-assembling solution;
(3) with 0.1g modification SiO
2Bead is ultrasonic to be scattered in the 25mL acetonitrile, adds the pre-assembling solution that 5mmolEGDMA, 0.125mmol AIBN and step (2) make, ice-bath ultrasonic 5min, logical N under the magnetic agitation
2Deoxygenation, temperature control adds thermal-initiated polymerization, and heating schedule is as follows: 50 ℃ of reaction 6h, be warming up to 60 ℃ of reaction 24h, be heated to 75 ℃ of reaction 6h again;
(5) reaction finishes the centrifugal supernatant of removing in back, use successively methyl alcohol-acetate (9: 1, v/v) solution, methyl alcohol supersound washing repeatedly detects less than template molecule through ultraviolet until supernatant;
(6) polymer globules that will remove template molecule places in the vacuum drying chamber, is dried to constant weight under 60 ℃, obtains the molecularly imprinted polymer bead.
Embodiment 7. preparation metsulfuron-methyl molecularly imprinted polymer on nano-silica gel surfaces SiO
2MSM-MIP 6
(1) with 0.2g SiO
2Bead is ultrasonic to be scattered in the 40mL toluene solution, adds 4mL γ-MPTS, logical N
2Deoxygenation, magnetic agitation 300rpm, 120 ℃ are reacted 12h down, and methyl alcohol supersound washing repeatedly is centrifugal, removes unreacted γ-MPTS, and 60 ℃ of following vacuum drying are to constant weight;
(2) 0.625mmol MSM, 2.5mmol MAA are added 25mL toluene-acetonitrile (4: 1, mix in v/v), fully shake up, place 4h, make pre-assembling solution;
(3) with 0.1g modification SiO
2Bead is ultrasonic be scattered in 25mL toluene-acetonitrile (4: 1, v/v) in, add the pre-assembling solution that 5mmol EGDMA, 0.125mmol AIBN and step (2) make, ice-bath ultrasonic 5min, logical N under the magnetic agitation
2Deoxygenation, temperature control adds thermal-initiated polymerization, and heating schedule is as follows: 50 ℃ of reaction 6h, be warming up to 60 ℃ of reaction 24h, be heated to 75 ℃ of reaction 6h again;
(5) reaction finishes the centrifugal supernatant of removing in back, use successively methyl alcohol-acetate (9: 1, v/v) solution, methyl alcohol supersound washing repeatedly detects less than template molecule through ultraviolet until supernatant;
(6) polymer globules that will remove template molecule places in the vacuum drying chamber, is dried to constant weight under 60 ℃, obtains the molecularly imprinted polymer bead.
The used polymer solvent of present embodiment is an optimum solvent.
(1) with 0.2g SiO
2Bead is ultrasonic to be scattered in the 40mL toluene solution, adds 4mL γ-MPTS, logical N
2Deoxygenation, magnetic agitation 300rpm, 120 ℃ are reacted 12h down, and methyl alcohol supersound washing repeatedly is centrifugal, removes unreacted γ-MPTS, and 60 ℃ of following vacuum drying are to constant weight;
(2) with mixing in 0.625mmol MSM, the 2.5mmol MAA adding 25mL chloroform, fully shake up, place 4h, make pre-assembling solution;
(3) with 0.1g modification SiO
2Bead is ultrasonic to be scattered in the 25mL chloroform, adds the pre-assembling solution that 5mmolEGDMA, 0.125mmol AIBN and step (2) make, ice-bath ultrasonic 5min, logical N under the magnetic agitation
2Deoxygenation, temperature control adds thermal-initiated polymerization, and heating schedule is as follows: 50 ℃ of reaction 6h, be warming up to 60 ℃ of reaction 24h, be heated to 75 ℃ of reaction 6h again;
(5) reaction finishes the centrifugal supernatant of removing in back, use successively methyl alcohol-acetate (9: 1, v/v) solution, methyl alcohol supersound washing repeatedly detects less than template molecule through ultraviolet until supernatant;
(6) polymer globules that will remove template molecule places in the vacuum drying chamber, is dried to constant weight under 60 ℃, obtains the molecularly imprinted polymer bead.
Embodiment 9. preparation metsulfuron-methyl molecularly imprinted polymer on nano-silica gel surfaces SiO
2MSM-MIP 8
(1) with 0.2g SiO
2Bead is ultrasonic to be scattered in the 40mL toluene solution, adds 4mL γ-MPTS, logical N
2Deoxygenation, magnetic agitation 300rpm, 120 ℃ are reacted 12h down, and methyl alcohol supersound washing repeatedly is centrifugal, removes unreacted γ-MPTS, and 60 ℃ of following vacuum drying are to constant weight;
(2) 0.625mmol MSM, 2.5mmol MAA are added 25mL toluene-acetonitrile (4: 1, mix in v/v), fully shake up, place 4h, make pre-assembling solution;
(3) with 0.1g modification SiO
2Bead is ultrasonic be scattered in 25mL toluene-acetonitrile (4: 1, v/v) in, add the pre-assembling solution that 5mmol DVB, 0.125mmol AIBN and step (2) make, ice-bath ultrasonic 5min, logical N under the magnetic agitation
2Deoxygenation, temperature control adds thermal-initiated polymerization, and heating schedule is as follows: 50 ℃ of reaction 6h, be warming up to 60 ℃ of reaction 24h, be heated to 75 ℃ of reaction 6h again;
(5) reaction finishes the centrifugal supernatant of removing in back, use successively methyl alcohol-acetate (9: 1, v/v) solution, methyl alcohol supersound washing repeatedly detects less than template molecule through ultraviolet until supernatant;
(6) polymer globules that will remove template molecule places in the vacuum drying chamber, is dried to constant weight under 60 ℃, obtains the molecularly imprinted polymer bead.
(1) with 0.2g SiO
2Bead is ultrasonic to be scattered in the 40mL toluene solution, adds 4mL γ-MPTS, logical N
2Deoxygenation, magnetic agitation 300rpm, 120 ℃ are reacted 12h down, and methyl alcohol supersound washing repeatedly is centrifugal, removes unreacted γ-MPTS, and 60 ℃ of following vacuum drying are to constant weight;
(2) 0.625mmol MSM, 2.5mmolMAA are added 25mL toluene-acetonitrile (4: 1, mix in v/v), fully shake up, place 4h, make pre-assembling solution;
(3) with 0.1g modification SiO
2Bead is ultrasonic be scattered in 25mL toluene-acetonitrile (4: 1, v/v) in, add the pre-assembling solution that 5mmol TRIM, 0.175mmol AIBN and step (2) make, ice-bath ultrasonic 5min, logical N under the magnetic agitation
2Deoxygenation, temperature control adds thermal-initiated polymerization, and heating schedule is as follows: 50 ℃ of reaction 6h, be warming up to 60 ℃ of reaction 24h, be heated to 75 ℃ of reaction 6h again;
(5) reaction finishes the centrifugal supernatant of removing in back, use successively methyl alcohol-acetate (9: 1, v/v) solution, methyl alcohol supersound washing repeatedly detects less than template molecule through ultraviolet until supernatant;
(6) polymer globules that will remove template molecule places in the vacuum drying chamber, is dried to constant weight under 60 ℃, obtains the molecularly imprinted polymer bead.
The selected crosslinking agent of present embodiment, initator are optimal conditions.
Embodiment 11. preparation metsulfuron-methyl molecularly imprinted polymer on nano-silica gel surfaces SiO
2MSM-MIP 10
(1) with 0.2g SiO
2Bead is ultrasonic to be scattered in the 40mL toluene solution, adds 4mL γ-MPTS, logical N
2Deoxygenation, magnetic agitation 300rpm, 120 ℃ are reacted 12h down, and methyl alcohol supersound washing repeatedly is centrifugal, removes unreacted γ-MPTS, and 60 ℃ of following vacuum drying are to constant weight;
(2) 0.625mmol MSM, 2.5mmol MAA are added 25mL toluene-acetonitrile (4: 1, mix in v/v), fully shake up, place 4h, make pre-assembling solution;
(3) with 0.1g modification SiO
2Bead is ultrasonic be scattered in 25mL toluene-acetonitrile (4: 1, v/v) in, add the pre-assembling solution that 5mmol TRIM, 0.175mmol BPO and step (2) make, ice-bath ultrasonic 5min, logical N under the magnetic agitation
2Deoxygenation, temperature control adds thermal-initiated polymerization, and heating schedule is as follows: 50 ℃ of reaction 6h, be warming up to 60 ℃ of reaction 24h, be heated to 75 ℃ of reaction 6h again;
(5) reaction finishes the centrifugal supernatant of removing in back, use successively methyl alcohol-acetate (9: 1, v/v) solution, methyl alcohol supersound washing repeatedly detects less than template molecule through ultraviolet until supernatant;
(6) polymer globules that will remove template molecule places in the vacuum drying chamber, is dried to constant weight under 60 ℃, obtains the molecularly imprinted polymer bead.
Embodiment 12. preparation metsulfuron-methyl molecularly imprinted polymer on nano-silica gel surfaces SiO
2MSM-MIP 11
(1) with 0.2g SiO
2Bead is ultrasonic to be scattered in the 40mL toluene solution, adds 4mL γ-MPTS, logical N
2Deoxygenation, magnetic agitation 300rpm, 120 ℃ are reacted 12h down, and methyl alcohol supersound washing repeatedly is centrifugal, removes unreacted γ-MPTS, and 60 ℃ of following vacuum drying are to constant weight;
(2) 0.625mmol MSM, 2.5mmol MAA are added 25mL toluene-acetonitrile (4: 1, mix in v/v), fully shake up, place 4h, make pre-assembling solution;
(3) with 0.1g modification SiO
2Bead is ultrasonic be scattered in 25mL toluene-acetonitrile (4: 1, v/v) in, add the pre-assembling solution that 5mmolTRIM, 0.175mmol ACVA and step (2) make, ice-bath ultrasonic 5min, logical N under the magnetic agitation
2Deoxygenation, temperature control adds thermal-initiated polymerization, and heating schedule is as follows: 50 ℃ of reaction 6h, be warming up to 60 ℃ of reaction 24h, be heated to 75 ℃ of reaction 6h again;
(5) reaction finishes the centrifugal supernatant of removing in back, use successively methyl alcohol-acetate (9: 1, v/v) solution, methyl alcohol supersound washing repeatedly detects less than template molecule through ultraviolet until supernatant;
(6) polymer globules that will remove template molecule places in the vacuum drying chamber, is dried to constant weight under 60 ℃, obtains the molecularly imprinted polymer bead.
Embodiment 13. preparation metsulfuron-methyl molecularly imprinted polymer on nano-silica gel surfaces SiO
2MSM-MIP 12
(1) with 0.2g SiO
2Bead is ultrasonic to be scattered in the 40mL toluene solution, adds 4mL γ-MPTS, logical N
2Deoxygenation, magnetic agitation 300rpm, 120 ℃ are reacted 12h down, and methyl alcohol supersound washing repeatedly is centrifugal, removes unreacted γ-MPTS, and 60 ℃ of following vacuum drying are to constant weight;
(2) 0.625mmol MSM, 1.25mmol MAA are added 25mL toluene-acetonitrile (4: 1, mix in v/v), fully shake up, place 4h, make pre-assembling solution;
(3) with 0.1g modification SiO
2Bead is ultrasonic be scattered in 25mL toluene-acetonitrile (4: 1, v/v) in, add the pre-assembling solution that 5mmol TRIM, 0.162mmol AIBN and step (2) make, ice-bath ultrasonic 5min, logical N under the magnetic agitation
2Deoxygenation, temperature control adds thermal-initiated polymerization, and heating schedule is as follows: 50 ℃ of reaction 6h, be warming up to 60 ℃ of reaction 24h, be heated to 75 ℃ of reaction 6h again;
(5) reaction finishes the centrifugal supernatant of removing in back, use successively methyl alcohol-acetate (9: 1, v/v) solution, methyl alcohol supersound washing repeatedly detects less than template molecule through ultraviolet until supernatant;
(6) polymer globules that will remove template molecule places in the vacuum drying chamber, is dried to constant weight under 60 ℃, obtains the molecularly imprinted polymer bead.
Embodiment 14. preparation metsulfuron-methyl molecularly imprinted polymer on nano-silica gel surfaces SiO
2MSM-MIP 13
(1) with 0.2g SiO
2Bead is ultrasonic to be scattered in the 40mL toluene solution, adds 4mL γ-MPTS, logical N
2Deoxygenation, magnetic agitation 300rpm, 120 ℃ are reacted 12h down, and methyl alcohol supersound washing repeatedly is centrifugal, removes unreacted γ-MPTS, and 60 ℃ of following vacuum drying are to constant weight;
(2) 0.625mmol MSM, 1.875mmol MAA are added 25mL toluene-acetonitrile (4: 1, mix in v/v), fully shake up, place 4h, make pre-assembling solution;
(3) with 0.1g modification SiO
2Bead is ultrasonic be scattered in 25mL toluene-acetonitrile (4: 1, v/v) in, add the pre-assembling solution that 5mmol TRIM, 0.169mmol AIBN and step (2) make, ice-bath ultrasonic 5min, logical N under the magnetic agitation
2Deoxygenation, temperature control adds thermal-initiated polymerization, and heating schedule is as follows: 50 ℃ of reaction 6h, be warming up to 60 ℃ of reaction 24h, be heated to 75 ℃ of reaction 6h again;
(5) reaction finishes the centrifugal supernatant of removing in back, use successively methyl alcohol-acetate (9: 1, v/v) solution, methyl alcohol supersound washing repeatedly detects less than template molecule through ultraviolet until supernatant;
(6) polymer globules that will remove template molecule places in the vacuum drying chamber, is dried to constant weight under 60 ℃, obtains the molecularly imprinted polymer bead.
Embodiment 15. preparation metsulfuron-methyl molecularly imprinted polymer on nano-silica gel surfaces SiO
2MSM-MIP 14
(1) with 0.2g SiO
2Bead is ultrasonic to be scattered in the 40mL toluene solution, adds 4mL γ-MPTS, logical N
2Deoxygenation, magnetic agitation 300rpm, 120 ℃ are reacted 12h down, and methyl alcohol supersound washing repeatedly is centrifugal, removes unreacted γ-MPTS, and 60 ℃ of following vacuum drying are to constant weight;
(2) 0.625mmol MSM, 3.125mmol MAA are added 25mL toluene-acetonitrile (4: 1, mix in v/v), fully shake up, place 4h, make pre-assembling solution;
(3) with 0.1g modification SiO
2Bead is ultrasonic be scattered in 25mL toluene-acetonitrile (4: 1, v/v) in, add the pre-assembling solution that 5mmol TRIM, 0.181mmol AIBN and step (2) make, ice-bath ultrasonic 5min, logical N under the magnetic agitation
2Deoxygenation, temperature control adds thermal-initiated polymerization, and heating schedule is as follows: 50 ℃ of reaction 6h, be warming up to 60 ℃ of reaction 24h, be heated to 75 ℃ of reaction 6h again;
(5) reaction finishes the centrifugal supernatant of removing in back, use successively methyl alcohol-acetate (9: 1, v/v) solution, methyl alcohol supersound washing repeatedly detects less than template molecule through ultraviolet until supernatant;
(6) polymer globules that will remove template molecule places in the vacuum drying chamber, is dried to constant weight under 60 ℃, obtains the molecularly imprinted polymer bead.
Embodiment 16. preparation metsulfuron-methyl molecularly imprinted polymer on nano-silica gel surfaces SiO
2MSM-MIP 15
(1) with 0.2g SiO
2Bead is ultrasonic to be scattered in the 40mL toluene solution, adds 4mL γ-MPTS, logical N
2Deoxygenation, magnetic agitation 300rpm, 120 ℃ are reacted 12h down, and methyl alcohol supersound washing repeatedly is centrifugal, removes unreacted γ-MPTS, and 60 ℃ of following vacuum drying are to constant weight;
(2) 0.625mmol MSM, 2.5mmol MAA are added 25mL toluene-acetonitrile (4: 1, mix in v/v), fully shake up, place 4h, make pre-assembling solution;
(3) with 0.1g modification SiO
2Bead is ultrasonic be scattered in 25mL toluene-acetonitrile (4: 1, v/v) in, add the pre-assembling solution that 2.5mmol TRIM, 0.1mmol AIBN and step (2) make, ice-bath ultrasonic 5min, logical N under the magnetic agitation
2Deoxygenation, temperature control adds thermal-initiated polymerization, and heating schedule is as follows: 50 ℃ of reaction 6h, be warming up to 60 ℃ of reaction 24h, be heated to 75 ℃ of reaction 6h again;
(5) reaction finishes the centrifugal supernatant of removing in back, use successively methyl alcohol-acetate (9: 1, v/v) solution, methyl alcohol supersound washing repeatedly detects less than template molecule through ultraviolet until supernatant;
(6) polymer globules that will remove template molecule places in the vacuum drying chamber, is dried to constant weight under 60 ℃, obtains the molecularly imprinted polymer bead.
The mol ratio of present embodiment template molecule, function monomer and crosslinking agent is a best proportion at 1: 4: 4, and gained molecularly imprinted polymer bead is optimum.
Embodiment 17. preparation metsulfuron-methyl molecularly imprinted polymer on nano-silica gel surfaces SiO
2MSM-MIP 16
(1) with 0.2g SiO
2Bead is ultrasonic to be scattered in the 40mL toluene solution, adds 4mL γ-MPTS, logical N
2Deoxygenation, magnetic agitation 300rpm, 120 ℃ are reacted 12h down, and methyl alcohol supersound washing repeatedly is centrifugal, removes unreacted γ-MPTS, and 60 ℃ of following vacuum drying are to constant weight;
(2) 0.625mmol MSM, 2.5mmol MAA are added 25mL toluene-acetonitrile (4: 1, mix in v/v), fully shake up, place 4h, make pre-assembling solution;
(3) with 0.1g modification SiO
2Bead is ultrasonic be scattered in 25mL toluene-acetonitrile (4: 1, v/v) in, add the pre-assembling solution that 10mmol TRIM, 0.325mmol AIBN and step (2) make, ice-bath ultrasonic 5min, logical N under the magnetic agitation
2Deoxygenation, temperature control adds thermal-initiated polymerization, and heating schedule is as follows: 50 ℃ of reaction 6h, temperature programming to 60 ℃ reaction 24h is heated to 75 ℃ of reaction 6h again;
(5) reaction finishes the centrifugal supernatant of removing in back, use successively methyl alcohol-acetate (9: 1, v/v) solution, methyl alcohol supersound washing repeatedly detects less than template molecule through ultraviolet until supernatant;
(6) polymer globules that will remove template molecule places in the vacuum drying chamber, is dried to constant weight under 60 ℃, obtains the molecularly imprinted polymer bead.
The test implementation example
Test implementation example 1. different molecular imprinted polymer beads are investigated the metsulfuron-methyl absorption property
With 20mg different molecular imprinted polymer microballoon (SiO
2MSM-MIP 1～16) in the ultrasonic respectively 5mL of the being scattered in concentration metsulfuron-methyl chloroformic solution that is 0.1mmol/L, airtight, room temperature jolting 30min, nylon membrane with 0.22 μ m after the adsorption equilibrium filters, quantitatively dilution, metsulfuron-methyl solution concentration before and after the ultraviolet-visible spectrophotometer is measured absorption in the 240nm place calculates equilibrium adsorption capacity Q according to formula (1)
e, operation repetitive three times.
In the formula, Q
e(mmol/g) be equilibrium adsorption capacity; V (L) is the volume of solution; C
0(mmol/L) be initial concentration of solution; C
e(mmol/L) be the equilibrium concentration of solution; M (g) is the quality of polymer.
Result of calculation shows, SiO
2The adsorbance of MSM-MIP 15 is maximum, 7.12 μ mol/g, the optimum condition that is the molecularly imprinted polymer microballoon is: the 4mL MPTS modification of 0.2g silica gel, function monomer is that MAA, crosslinking agent are that TRIM, initator are that AIBN, solvent are toluene-acetonitrile (4: 1 during polymerization, v/v), the mol ratio of template molecule, function monomer and crosslinking agent is 1: 4: 4.
The 2. static adsorption tests of test implementation example
Precision takes by weighing 13 parts of 20mg SiO
2MSM-MIP 15 and SiO
2MSM-NIP 15, in the metsulfuron-methyl chloroformic solution that the ultrasonic respectively 5mL of being scattered in series concentration is 0.1～5mmol/L, airtight, room temperature jolting 30min, nylon membrane with 0.22 μ m after the adsorption equilibrium filters, metsulfuron-methyl solution concentration before and after quantitatively dilution, ultraviolet-visible spectrophotometer are measured absorption in the 240nm place calculates equilibrium adsorption capacity Q according to formula (1)
e, operation repetitive three times.
The result as shown in Figure 3, the adsorbance of MIP is much larger than NIP, the greatest differences on this adsorbance is that MIP is different from physical absorption to the absorption of metsulfuron-methyl by the absorption principle decision of material itself, but a kind of selective absorption that the specific recognition site is arranged.Because molecularly imprinted polymer is a Nano microsphere, and surface area is big, its maximal absorptive capacity reaches 103.35 μ mol/g in addition.With silica gel is core, and rigidity is higher, and polymer stabilizing is good, still can keep its more stable adsorbance after reusing 10 times, and this also is positioned at the surface from another side explanation polymer in conjunction with the site, makes the template wash-out thorough easily.
Test implementation example 3. dynamic adsorption tests
Precision takes by weighing 13 parts of 20mg SiO
2MSM-MIP 15, in the metsulfuron-methyl chloroformic solution that the ultrasonic respectively 5mL of being scattered in concentration is 2mmol/L, airtight, the room temperature jolting, nylon membrane 5,10,15,20,25,30,60,120, with 0.22 μ m behind the 180min filters respectively, metsulfuron-methyl solution concentration before and after quantitatively dilution, ultraviolet-visible spectrophotometer are measured absorption in the 240nm place calculates equilibrium adsorption capacity Q according to formula (1)
e, operation repetitive three times.
The result as shown in Figure 4, MIP can reach adsorption equilibrium rapidly in 25min.This quick adsorption capacity can think that binding site is positioned at the silica gel surface owing to the core-shell structure of molecularly imprinted polymer, and template molecule binding ability again is strong.
Test implementation example 4. selective absorptions test
Precision takes by weighing 5 parts of 20mg SiO
2MSM-MIP 15 and SiO
2MSM-NIP 15, the metsulfuron-methyl that the ultrasonic respectively 5mL of being scattered in concentration is 2mmol/L, chlorine sulphur are grand, in the bensulfuron-methyl, tribenuron-methyl, chlopyrifos chloroformic solution, airtight, room temperature jolting 30min, nylon membrane with 0.22 μ m after the adsorption equilibrium filters, quantitatively dilution, target molecule solution concentration before and after the absorption of ultraviolet-visible spectrophotometric determination calculates equilibrium adsorption capacity Q according to formula (1)
e, operation repetitive three times.
The result as shown in Figure 5, SiO
215 pairs of sulfonylurea herbicides of MSM-MIP have higher selectivity, and to the no specific adsorption of organophosphorus insecticide chlopyrifos (CPF).This is because the chlopyrifos structure is different from sulfonylurea pesticide fully; And chlorine sulphur grand (CS), bensulfuron-methyl (BSM), tribenuron-methyl (TBM) and metsulfuron-methyl (MSM) structure are similar.As seen resulting polymers has high selectivity to template molecule and analog thereof, and this selectivity is based on the matched of marking site and space conformation.
Claims (7)
1. the preparation method of a molecularly imprinted polymer on nano-silica gel surfaces of sulfonylurea herbicides comprises SiO
2The preparation of bead: with the absolute ethyl alcohol is solvent, and concentrated ammonia liquor is a catalyst, and positive tetraethyl orthosilicate is silicon source synthesis of nano SiO
2Bead, supersound washing is extremely neutral, centrifugal repeatedly with absolute ethyl alcohol, is dried to constant weight, and is standby, it is characterized in that preparation process is:
(1) with the SiO that makes
2Bead is ultrasonic to be dispersed in γ-methacryloxypropyl trimethoxy silane toluene solution of 10% (v/v), logical N
2Deoxygenation is stirred, and 100～120 ℃ are reacted 12～24h down, centrifugal, obtains the SiO of surface modification
2Bead, centrifugal by the methyl alcohol supersound washing, remove unreacted γ-methacryloxypropyl trimethoxy silane, centrifugal, products therefrom is dried to constant weight;
(2) template molecule, function monomer are added polymer solvent, fully shake up and make pre-assembling solution;
(3) the modification SiO that step (1) is made
2Bead is ultrasonic to be scattered in the polymer solvent, adds the pre-assembling solution that crosslinking agent, initator and step (2) make, and, stirs logical N with gained mixed liquor ice-bath ultrasonic
2Deoxygenation is at N
2Temperature control adds thermal-initiated polymerization under the atmosphere;
(4) the centrifugal supernatant of removing after the polymerisation is used methyl alcohol-acetic acid solution, methyl alcohol supersound washing successively, detects less than template molecule through ultraviolet until supernatant; Methyl alcohol in described methyl alcohol-acetic acid solution: the volume ratio of acetate is 9: 1;
(5) polymer globules that will remove template molecule is dried to constant weight, obtains the molecularly imprinted polymer bead.
2. the preparation method of molecularly imprinted polymer on nano-silica gel surfaces of sulfonylurea herbicides according to claim 1 is characterized in that: described SiO
2The preparation method of bead is: absolute ethyl alcohol and concentrated ammonia liquor are mixed according to volume ratio at 50: 9, get solution A; Again absolute ethyl alcohol and positive tetraethyl orthosilicate are mixed according to volume ratio at 6: 1, get solution B; Under the room temperature solution B is added with 10～15 droplets/second speed Continuous Titration in the solution A that stirs, when the volume ratio of solution A and solution B is 59: 35, continue to stir 24h after titration finishes; Supersound washing is to neutral repeatedly with absolute ethyl alcohol, and centrifugal, 60 ℃ of following vacuum drying are to constant weight.
3. the preparation method of molecularly imprinted polymer on nano-silica gel surfaces of sulfonylurea herbicides according to claim 1 is characterized in that: in the described step (1), and nanometer SiO
2The mass ratio of bead, γ-methacryloxypropyl trimethoxy silane 1: 10～1: 30.
4. the preparation method of molecularly imprinted polymer on nano-silica gel surfaces of sulfonylurea herbicides according to claim 1, it is characterized in that: in the described step (2), template molecule is a metsulfuron-methyl, function monomer is a methacrylic acid, and polymer solvent is that acetonitrile, volume ratio are toluene-acetonitrile mixed liquor or chloroform of 4: 1; The mol ratio of template molecule and function monomer is 1: 2～1: 5.
5. the preparation method of molecularly imprinted polymer on nano-silica gel surfaces of sulfonylurea herbicides according to claim 1 is characterized in that: in the described step (3), and modification SiO
2The consumption of bead is the corresponding 0.625mmol template molecule of 0.1g bead, corresponding 50mL polymer solvent.
6. the preparation method of molecularly imprinted polymer on nano-silica gel surfaces of sulfonylurea herbicides according to claim 1, it is characterized in that: in the described step (3), template molecule and crosslinking agent mol ratio are 1: 4～1: 16.
7. the preparation method of molecularly imprinted polymer on nano-silica gel surfaces of sulfonylurea herbicides according to claim 1, it is characterized in that: in the described step (3), temperature control adds thermal-initiated polymerization, and heating schedule is as follows: 50 ℃ of reaction 6h, be warming up to 60 ℃ of reaction 24h, be heated to 75 ℃ of reaction 6h again.
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