A magnetic surface molecularly imprinted polymer and its preparation method and application

Abstract

The invention provides a magnetic surface molecularly imprinted polymer and its preparation method and application. Using magnetic mesoporous titanium dioxide as a carrier, the surface of the carrier is firstly modified by azido-functionalized dopamine, and then the RAFT reagent is modified by click chemistry. to the surface of the carrier, and finally undergo RAFT polymerization to obtain a magnetic surface molecularly imprinted polymer; the present invention prepares a molecularly imprinted polymer layer through surface-induced reversible addition-fragmentation chain transfer active radical polymerization; the prepared magnetic surface molecularly imprinted polymer The object shows a regular spherical structure and good dispersion and has an obvious multilayer core-shell structure; the present invention combines the characteristics of mesopority, high specific surface area and good magnetic responsiveness of the carrier; the magnetic surface molecule of the present invention In the presence of structural analogues, the imprinted polymer exhibits a good selective recognition function for the target molecule TBBPA, and has broad application prospects in the recognition and detection of TBBPA in environmental systems.

Description

technical field

[0001] The invention belongs to the technical field of molecularly imprinted polymers, in particular to a magnetic surface molecularly imprinted polymer and its preparation method and application. Background technique

[0002] Molecularly imprinted polymers (MIPs) are receptors with special affinity and specific recognition function for target compounds. Due to their specific recognition function, MIPs have a wide range of applications in the field of chemical / biological sensors. Bulk polymerization is a traditional method for preparing molecularly imprinted polymers. The molecularly imprinted polymers prepared by this method often have to go through steps such as grinding and sieving. The preparation process is cumbersome, and a large number of recognition sites are embedded, resulting in low recognition efficiency. There is a risk of template molecules leaking during use, which will affect the detection results.

[0003] Surface imprinting refers to impri...

Examples

preparation example Construction

[0035] The present invention also provides a method for preparing a molecularly imprinted polymer on a magnetic surface, comprising the following steps:

[0036] Step 1, prepare Fe by solvothermal method 3 o 4 magnetic nanoparticles;

[0037] Step 2, by sol-gel method in Fe 3 o 4 The surface of the magnetic nanoparticles is coated with silica, and the magnetic nanospheres coated with silica are obtained. 3 o 4 @SiO 2 ;

[0038] Step 3, the magnetic nano-microspheres Fe coated with silicon dioxide 3 o 4 @SiO 2 Disperse in absolute ethanol, add ammonia water and tetrabutyl titanate, and carry out hydrolysis reaction to obtain magnetic nanospheres Fe coated with titanium dioxide. 3 o 4 @TiO 2 ; Then through magnetic separation, washing, drying and heat treatment, the magnetic mesoporous titania nanosphere Fe 3 o 4 @mTiO 2 ;

[0039] Step 4, the magnetic mesoporous titania nano-microspheres Fe 3 o 4 @mTiO 2 Ultrasonic dispersion into anhydrous dichloromethane, a...

Embodiment 1

[0047] This example describes in detail the preparation method of molecularly imprinted polymers on magnetic surfaces, as shown in the attached figure 1 shown, with figure 1 It is a schematic diagram of the preparation process of the molecularly imprinted polymer on the magnetic surface of the present invention; the specific steps in this embodiment are as follows:

[0048] Step 1, adopt solvothermal method to prepare Fe 3 o 4 magnetic nanoparticles;

[0049] Specifically, first, weigh 2.6g anhydrous ferric trichloride, 1.0g sodium citrate and 4.0g anhydrous sodium acetate; dissolve the weighed anhydrous ferric chloride, sodium citrate and anhydrous sodium acetate in In 80mL ethylene glycol, sonicate for 15-30min to fully dissolve and obtain a uniform solution;

[0050] Then, pour the above homogeneous solution into a stainless steel autoclave for reaction; wherein, the reaction temperature is 180-200°C, and the reaction time is 10-24h; after the reaction is completed, coo...

Embodiment 2

[0098] The steps of this embodiment are substantially the same as those of Embodiment 1, except that the ratio of 4-vinylpyridine to ethylene glycol dimethacrylate in step 6 is different.

[0099] Specifically, in step 6, dissolve 0.21g of 4-vinylpyridine and TBBPA in 50mL of anhydrous toluene, and mechanically stir for 12-24h under the protection of nitrogen; add 50mg of RAFT reagent-modified magnetic mesoporous titanium dioxide carrier Fe 3 o 4 @mTiO 2 -CPDB, which is dispersed in the above solution; then add 0.369g ethylene glycol dimethacrylate and 20mg azobisisobutyronitrile, and carry out polymerization reaction under nitrogen atmosphere to obtain the reaction product; adopt ethanol to carry out the reaction product Washing, vacuum drying to obtain the magnetic surface molecularly imprinted polymer Fe 3 o 4 @mTiO 2 @MIP; where the polymerization temperature is 60-70°C and the reaction time is 16-32h. The imprinted polymers obtained at different ratios showed differe...

technical field

[0001] The invention belongs to the technical field of molecularly imprinted polymers, in particular to a magnetic surface molecularly imprinted polymer and its preparation method and application. Background technique

[0002] Molecularly imprinted polymers (MIPs) are receptors with special affinity and specific recognition function for target compounds. Due to their specific recognition function, MIPs have a wide range of applications in the field of chemical / biological sensors. Bulk polymerization is a traditional method for preparing molecularly imprinted polymers. The molecularly imprinted polymers prepared by this method often have to go through steps such as grinding and sieving. The preparation process is cumbersome, and a large number of recognition sites are embedded, resulting in low recognition efficiency. There is a risk of template molecules leaking during use, which will affect the detection results.

[0003] Surface imprinting refers to impri...

Examples

preparation example Construction

[0035] The present invention also provides a method for preparing a molecularly imprinted polymer on a magnetic surface, comprising the following steps:

[0036] Step 1, prepare Fe by solvothermal method 3 o 4 magnetic nanoparticles;

[0037] Step 2, by sol-gel method in Fe 3 o 4 The surface of the magnetic nanoparticles is coated with silica, and the magnetic nanospheres coated with silica are obtained. 3 o 4 @SiO 2 ;

[0038] Step 3, the magnetic nano-microspheres Fe coated with silicon dioxide 3 o 4 @SiO 2 Disperse in absolute ethanol, add ammonia water and tetrabutyl titanate, and carry out hydrolysis reaction to obtain magnetic nanospheres Fe coated with titanium dioxide. 3 o 4 @TiO 2 ; Then through magnetic separation, washing, drying and heat treatment, the magnetic mesoporous titania nanosphere Fe 3 o 4 @mTiO 2 ;

[0039] Step 4, the magnetic mesoporous titania nano-microspheres Fe 3 o 4 @mTiO 2 Ultrasonic dispersion into anhydrous dichloromethane, a...

Embodiment 1

[0047] This example describes in detail the preparation method of molecularly imprinted polymers on magnetic surfaces, as shown in the attached figure 1 shown, with figure 1 It is a schematic diagram of the preparation process of the molecularly imprinted polymer on the magnetic surface of the present invention; the specific steps in this embodiment are as follows:

[0048] Step 1, adopt solvothermal method to prepare Fe 3 o 4 magnetic nanoparticles;

[0049] Specifically, first, weigh 2.6g anhydrous ferric trichloride, 1.0g sodium citrate and 4.0g anhydrous sodium acetate; dissolve the weighed anhydrous ferric chloride, sodium citrate and anhydrous sodium acetate in In 80mL ethylene glycol, sonicate for 15-30min to fully dissolve and obtain a uniform solution;

[0050] Then, pour the above homogeneous solution into a stainless steel autoclave for reaction; wherein, the reaction temperature is 180-200°C, and the reaction time is 10-24h; after the reaction is completed, coo...

Embodiment 2

[0098] The steps of this embodiment are substantially the same as those of Embodiment 1, except that the ratio of 4-vinylpyridine to ethylene glycol dimethacrylate in step 6 is different.

[0099] Specifically, in step 6, dissolve 0.21g of 4-vinylpyridine and TBBPA in 50mL of anhydrous toluene, and mechanically stir for 12-24h under the protection of nitrogen; add 50mg of RAFT reagent-modified magnetic mesoporous titanium dioxide carrier Fe 3 o 4 @mTiO 2 -CPDB, which is dispersed in the above solution; then add 0.369g ethylene glycol dimethacrylate and 20mg azobisisobutyronitrile, and carry out polymerization reaction under nitrogen atmosphere to obtain the reaction product; adopt ethanol to carry out the reaction product Washing, vacuum drying to obtain the magnetic surface molecularly imprinted polymer Fe 3 o 4 @mTiO 2 @MIP; where the polymerization temperature is 60-70°C and the reaction time is 16-32h. The imprinted polymers obtained at different ratios showed differe...

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