CN109021171B - Aqueous preparation method of tylosin tartrate surface molecularly imprinted polymer and its application - Google Patents

Abstract

The invention discloses an aqueous phase preparation method and application of a molecularly imprinted polymer on the surface of tylosin tartrate, and belongs to the technical field of sample pretreatment and pollutant analysis and detection. The main point of the technical solution of the present invention is: take 2-acrylamide-2-methylpropanesulfonic acid and/or 1,4-butanediyl-3,3'-bis-1-vinylimidazolium chloride as functional monomer , tylosin tartrate is the template molecule, pure water is the preparation solvent, and the polymerization reaction is thermally initiated by the cross-linking agent N,N'-methylenebisacrylamide and the initiator azobisisobutyronitrile. Preparation of tylosin tartrate surface molecularly imprinted polymer on the surface of vinylbenzene particle carrier Trace levels of tylosin tartrate in environmental samples. The invention has the advantages of simple preparation process and low cost, uniform particle size of the polymer adsorbent material, large adsorption capacity and high mass transfer rate.

Description

Aqueous preparation method of tylosin tartrate surface molecularly imprinted polymer and the same application

technical field

The invention belongs to the technical field of sample pretreatment and pollutant analysis and detection, and further belongs to the technical field of preparation of novel surface molecularly imprinted polymers for macrolide antibiotics, in particular to a surface molecularly imprinted polymer of tylosin tartrate A method for the preparation of an aqueous phase of a substance and its application.

Background technique

Antibiotics have broad antibacterial spectrum, low price and wide application. With its rapid development, its pollution problem has become more and more prominent. Conventional treatment technology cannot completely remove it, and its trace residues in complex environmental media will cause great harm to the ecosystem and human health.

Macrolide antibiotics are a general term for antibiotics with a macrolactone ring skeleton structure, which are widely used in human medicine and veterinary medicine by inhibiting the synthesis of bacterial proteins, thereby resisting Gram-positive and gram-negative bacteria. One of the fastest growing antibiotics in the world in both demand and sales. The drug residues and environmental exposure caused by its large-scale use affect the export trade of animal food in my country on the one hand, and also pose a great potential threat to human health and the ecosystem on the other hand. Therefore, it is urgent to strengthen its analysis and detection in environmental media. , for the effective monitoring of trace antibiotics in complex environments.

However, the content of antibiotics in the environmental medium is low, the environmental matrix is complex, and the interference is serious, which often leads to large errors in the analytical testing process, so sample pretreatment has become an essential procedure for its effective monitoring.

At present, the more commonly used sample pretreatment methods are: solid-phase extraction, pressurized solvent extraction, solid-phase microextraction and matrix solid-phase dispersion, etc. Although they can meet the analysis requirements of most samples, the complex matrix Interference still affects the separation and analysis of low-concentration target compounds, so it is urgent to develop specific and highly selective pretreatment methods, which are of great significance for the separation and analysis of trace antibiotics in complex environments.

Molecular imprinting, also known as molecular imprinting, refers to a technology that uses a specific target molecule as a template to prepare a polymer with specific recognition ability. The obtained polymer-molecularly imprinted polymer can specifically recognize target molecules due to the existence of three-dimensional holes and specific functional groups, and integrates separation and enrichment. It has the advantages of simple preparation, low cost, high selectivity, good stability, high mechanical strength, and recyclability, and has attracted much attention in sample pretreatment.

However, most of the current molecularly imprinted polymers are prepared in toxic organic solvents such as acetonitrile, chloroform, and toluene. In order to avoid secondary pollution caused by highly toxic organic solvents, how to realize the preparation of molecularly imprinted polymers in green medium water has become a research topic. hot spot.

Non-covalently bonded molecularly imprinted polymers are widely used because of their easy identification and elution characteristics. They are mainly used for specific binding to targets through hydrogen bonding, van der Waals forces, and electrostatic forces. In order to prepare non-covalently bonded imprinted polymers in aqueous phase, the interference of intermolecular hydrogen bonds of water must be overcome. Based on the outstanding feature of strong designability of ionic liquids, the present invention designs and synthesizes ionic liquid polymers with various specific functional groups and uses them as functional monomers, so as to enhance the strength of their interaction with target molecules and improve the selective adsorption of imprinted polymers. The ability to finally realize the preparation of green solvent water imprinted polymers.

In the present invention, 2-acrylamide-2-methylpropanesulfonic acid and/or 1,4-butanediyl-3,3'-bis-1-vinylimidazole chloride are used as functional monomers, and pure water is used as preparation solvent , tylosin tartrate, a typical drug in macrolide antibiotics, is a template molecule, and N,N'-methylenebisacrylamide is a cross-linking agent, and surface molecules are prepared on the surface of the styrene-divinylbenzene particle carrier. Imprinted polymeric adsorbent material. At present, there is no literature report on the preparation of the surface molecularly imprinted polymer material by this method, and the imprinted polymer material prepared by the surface polymerization method has a regular shape, a fast mass transfer rate and a good regeneration effect.

SUMMARY OF THE INVENTION

The technical problem solved by the present invention is to provide a water-phase preparation of tylosin tartrate surface molecularly imprinted polymer prepared in a green solvent with ionic liquid as functional monomer and having specific adsorption performance for tylosin tartrate According to the method, the surface molecularly imprinted polymer of tylosin tartrate prepared by the method has a specific recognition effect on the target molecule tylosin tartrate.

The present invention adopts the following technical scheme in order to solve the above-mentioned technical problems, the water phase preparation method of tylosin tartrate surface molecularly imprinted polymer is characterized in that: with 2-acrylamide-2-methylpropanesulfonic acid and/or 1, 4-Butanediyl-3,3'-bis-1-vinylimidazolium chloride is the functional monomer, tylosin tartrate is the template molecule, and pure water is the preparation solvent. Surface molecular imprinting of tylosin tartrate with specific recognition ability for tylosin tartrate prepared on the surface of styrene-divinylbenzene particle carrier by thermally-initiated polymerization of methylbisacrylamide and initiator azobisisobutyronitrile polymer.

Preferably, the molar ratio of the template molecule, the functional monomer, the crosslinking agent and the initiator is 1:4-8:10-20:0.12.

Preferably, the water phase preparation method of the molecularly imprinted polymer on the surface of tylosin tartrate is characterized in that the specific steps are: adding template molecule tylosin tartrate, 0.15g carrier styrene-dicarbonate into 30mL pure water solvent Vinylbenzene particles and functional monomers 2-acrylamido-2-methylpropanesulfonic acid and/or 1,4-butanediyl-3,3'-bis-1-vinylimidazole chloride, pre-treated at 30°C After 4 hours of polymerization, the cross-linking agent N,N'-methylenebisacrylamide and the initiator azobisisobutyronitrile were added, wherein the molar ratio of template molecule, functional monomer, cross-linking agent and initiator was 1:6 : 15:0.12, then thermally initiate the polymerization reaction at 60 °C for 24 h, extract the template molecules with a methanol/acetic acid mixture with a volume ratio of 8-9:2-1 for 48 h to elute the template molecules, and then rinse with methanol at 60 ℃ vacuum drying to obtain the surface molecularly imprinted polymer of tylosin tartrate.

The tylosin tartrate surface molecularly imprinted polymer of the invention has an action site with specific recognition performance for tylosin tartrate, and can be used for selectively adsorbing trace amounts of tylosin tartrate in environmental samples.

After analysis, the polymer adsorbent material prepared by the present invention has an action site with specific recognition performance for tylosin tartrate. In order to verify the existence of a selective adsorption site for tylosin tartrate, the traditional UV-visible spectrophotometry was used to verify and detect trace amounts of tylosin tartrate by high performance liquid chromatography.

Compared with the prior art, the present invention has the following beneficial effects:

1. The present invention provides a simple preparation process, low cost, 2-acrylamide-2-methylpropanesulfonic acid and/or 1,4-butanediyl-3,3'-bis-1-vinyl The imidazolium chloride salt is a surface molecularly imprinted polymer adsorbent material of functional monomer. The polymer adsorbent material has regular shape, uniform particle size, large adsorption capacity and high mass transfer rate.

2. The surface polymerization method preferably adopted in the present invention overcomes the inherent defects of bulk polymerization, emulsion polymerization and precipitation polymerization, and has the excellent properties of uniform particle size, fast mass transfer rate, and easy adsorption and elution. In addition, polymers prepared by surface polymerization have broader application prospects.

3. The present invention preferentially uses 2-acrylamido-2-methylpropanesulfonic acid and 1,4-butanediyl-3,3'-bis-1-vinylimidazole chloride as functional monomers in the aqueous phase. It is formed by thermal initiation of polymerization at 60°C. Compared with the previous toxic organic solvents such as acetonitrile and chloroform, the preparation of aqueous phase greatly reduces the pollution of the solvent to the environment, and uses ionic liquids as functional monomers, through π-π bonds, hydrogen bonds and static electricity and other forms of action. The force forms a complex with the template molecule, which overcomes the interference of intermolecular hydrogen bonds of water, and lays a foundation for the synthesis of surface molecularly imprinted polymers in polar media such as water.

4. According to a preferred embodiment of the present invention, pure water is used as the preparation solvent, styrene-divinylbenzene particles are used as the carrier, tylosin tartrate is used as the template molecule, and 2-acrylamide-2-methylpropane is used as the preparation solvent. Sulfonic acid and/or 1,4-butanediyl-3,3'-bis-1-vinylimidazole chloride are functional monomers, and N,N'-methylenebisacrylamide is a cross-linking agent. Under the action of azobisisobutyronitrile, thermally-initiated polymerization was obtained to obtain a surface molecularly imprinted polymer with uniform particle size and specific adsorption performance for tylosin tartrate. The surface molecularly imprinted polymer had excellent selective adsorption performance (maximum adsorption capacity). The capacity is 142.65mg g ^-1 ), which can be used for the separation and enrichment of trace tylosin tartrate in actual environmental samples.

Detailed ways

The above-mentioned content of the present invention is described in further detail below through the examples, but it should not be understood that the scope of the above-mentioned subject matter of the present invention is limited to the following examples, and all technologies realized based on the above-mentioned content of the present invention belong to the scope of the present invention.

Example 1

Using 30mL pure water as solvent, tylosin tartrate as template molecule, 0.15g styrene-divinylbenzene particles as carrier, 2-acrylamide-2-methylpropanesulfonic acid and 1,4-butanediyl- 3,3'-bis-1-vinylimidazolium chloride as functional monomer, prepolymerized at 30℃ for 4h, added crosslinker N,N'-methylenebisacrylamide and initiator azobisisobutyronitrile , wherein the molar ratio of template molecule, functional monomer, crosslinking agent and initiator is 1:4:20:0.12, and then thermally initiate the polymerization reaction at 60°C for 24h, using a methanol/acetic acid mixture with a volume ratio of 8:2 The template molecules were eluted by Soxhlet extraction for 48 hours, rinsed with methanol, and then dried under vacuum at 60 °C to obtain the surface molecularly imprinted polymer of tylosin tartrate. specific adsorption properties.

Example 2

Using 30mL pure water as solvent, tylosin tartrate as template molecule, 0.15g styrene-divinylbenzene particles as carrier, 2-acrylamide-2-methylpropanesulfonic acid and 1,4-butanediyl- 3,3'-bis-1-vinylimidazolium chloride as functional monomer, prepolymerized at 30℃ for 4h, added crosslinker N,N'-methylenebisacrylamide and initiator azobisisobutyronitrile , wherein the molar ratio of template molecule, functional monomer, cross-linking agent and initiator is 1:8:20:0.12, and then thermally initiate the polymerization reaction at 60 °C for 24h, using a methanol/acetic acid mixture with a volume ratio of 8:2 The template molecules were eluted by Soxhlet extraction for 48 hours, rinsed with methanol, and then dried under vacuum at 60 °C to obtain the surface molecularly imprinted polymer of tylosin tartrate. specific adsorption properties.

Example 3

Using 30mL pure water as solvent, tylosin tartrate as template molecule, 0.15g styrene-divinylbenzene particles as carrier, 2-acrylamide-2-methylpropanesulfonic acid and 1,4-butanediyl- 3,3'-bis-1-vinylimidazolium chloride as functional monomer, prepolymerized at 30℃ for 4h, added crosslinker N,N'-methylenebisacrylamide and initiator azobisisobutyronitrile , wherein the molar ratio of template molecule, functional monomer, cross-linking agent and initiator is 1:6:10:0.12, and then thermally initiate the polymerization reaction at 60 °C for 24h, using a methanol/acetic acid mixture with a volume ratio of 8:2 The template molecules were eluted by Soxhlet extraction for 48 hours, rinsed with methanol, and then dried under vacuum at 60 °C to obtain the surface molecularly imprinted polymer of tylosin tartrate. Specific adsorption properties.

Example 4

Using 30mL pure water as solvent, tylosin tartrate as template molecule, 0.15g styrene-divinylbenzene particles as carrier, 2-acrylamide-2-methylpropanesulfonic acid and 1,4-butanediyl- 3,3'-bis-1-vinylimidazolium chloride as functional monomer, prepolymerized at 30℃ for 4h, added crosslinker N,N'-methylenebisacrylamide and initiator azobisisobutyronitrile , in which the molar ratio of template molecule, functional monomer, cross-linking agent and initiator is 1:6:15:0.12, and then thermally initiate the polymerization reaction at 60 °C for 24h, using a methanol/acetic acid mixture with a volume ratio of 8:2 The template molecules were eluted by Soxhlet extraction for 48 hours, rinsed with methanol, and then dried under vacuum at 60 °C to obtain the surface molecularly imprinted polymer of tylosin tartrate. specific adsorption properties.

Example 5

Using 30mL pure water as solvent, tylosin tartrate as template molecule, 0.15g styrene-divinylbenzene particles as carrier, 2-acrylamide-2-methylpropanesulfonic acid and 1,4-butanediyl- 3,3'-bis-1-vinylimidazolium chloride as functional monomer, prepolymerized at 30℃ for 4h, added crosslinker N,N'-methylenebisacrylamide and initiator azobisisobutyronitrile , wherein the molar ratio of template molecule, functional monomer, crosslinking agent and initiator is 1:6:15:0.12, and then thermally initiate the polymerization reaction at 60°C for 24h, using a methanol/acetic acid mixture with a volume ratio of 9:1 The template molecules were eluted by Soxhlet extraction for 48 hours, rinsed with methanol, and then dried under vacuum at 60 °C to obtain the surface molecularly imprinted polymer of tylosin tartrate. specific adsorption properties.

Example 6

10 mg of tylosin tartrate surface molecularly imprinted polymer and non-imprinted polymer prepared in Example 4 were taken, respectively added to 10 mL of 0.1 mmolL ^-1 aqueous solution of tylosin tartrate, and shaken at room temperature for 3 hours. The results of UV spectroscopy showed that the adsorption capacity of the molecularly imprinted polymer on the surface of tylosin tartrate to tylosin tartrate could reach 48.07μmol g ^-1 , and the adsorption capacity of the corresponding non-imprinted polymer to tylosin tartrate was only 48.07 μmol g -1 . 1.44μmol g ^-1 , indicating that the surface molecularly imprinted polymer of tylosin tartrate has good adsorption performance for tylosin tartrate.

Example 7

Get the tylosin tartrate surface molecularly imprinted polymer and the non-imprinted polymer that 10mg embodiment 4 prepares, join respectively the tylosin tartrate, guitarmycin tartrate, tilmicosin phosphate of 10mL 0.1mmol L ^-1 In aqueous solution, shake at room temperature for 3h. The results of UV spectrum detection showed that the adsorption capacities of the molecularly imprinted polymers on the surface of tylosin tartrate to the above substrates were 36.92 μmol g ^-1 , 36.00 μmol g ^-1 , and 20.96 μmol g ^-1 , respectively. The adsorption capacity of all compounds was lower than 5.55μmol g ^-1 , which indicated that the prepared tylosin tartrate surface molecularly imprinted polymer also had good adsorption capacity for structural analogs of template molecules.

Example 8

Get the tylosin tartrate surface molecularly imprinted polymer and the non-imprinted polymer that 10mg embodiment 4 makes, join respectively the tylosin tartrate, ciprofloxacin hydrochloride, phenformin hydrochloride of 10mL 0.1mmol L ^-1 , metronidazole and amoxicillin sodium aqueous solution, shake at room temperature for 3h. The results of UV spectroscopy showed that the adsorption capacity of tylosin tartrate surface molecularly imprinted polymer on tylosin tartrate was 36.56μmol g ^-1 , and the adsorption capacity of non-imprinted polymer on tylosin tartrate was less than 2μmol g ^{- 1} ; while the molecularly imprinted polymer and non-imprinted polymer on the surface of tylosin tartrate were all less than 3.50μmol g ^-1 for adsorption of ciprofloxacin hydrochloride, phenformin hydrochloride, metronidazole and amoxicillin sodium, It shows that the prepared tylosin tartrate surface molecularly imprinted polymer has a specific recognition effect on tylosin tartrate.

Example 9

The surface molecularly imprinted polymer of tylosin tartrate prepared in Example 4 is used as a filler to make a solid phase extraction small column, which is used for the separation and enrichment of the detection of trace residual macrolide pollutants in actual wastewater and animal food. The results of the standard addition experiment showed that the recovery rate reached more than 90%, indicating that the obtained tylosin tartrate surface molecularly imprinted polymer had good practicability; after more than 30 cycles of use, the adsorption of the solid phase extraction cartridge There was no obvious decrease in performance, indicating that the obtained tylosin tartrate surface molecularly imprinted polymer had good cycling stability.

The above embodiments describe the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above embodiments. The above embodiments and descriptions only describe the principles of the present invention. Without departing from the scope of the principles of the present invention, the present invention may have various changes and improvements, and these changes and improvements all fall within the protection scope of the present invention.

Claims (3)

1. the water-phase preparation method of tylosin tartrate surface molecularly imprinted polymer is characterized in that: with 2-acrylamide-2-methylpropanesulfonic acid and 1,4-butanediyl-3,3'-bis -1-Vinylimidazolium chloride is the functional monomer, tylosin tartrate is the template molecule, and pure water is the preparation solvent. Nitrile thermally initiates a polymerization reaction to prepare a surface molecularly imprinted polymer of tylosin tartrate with specific recognition ability for tylosin tartrate on the surface of the styrene-divinylbenzene particle carrier. The template molecules, functional monomers, The molar ratio of the crosslinking agent to the initiator is 1:4-8:10-20:0.12. 2. the water-phase preparation method of tylosin tartrate surface molecularly imprinted polymer according to claim 1, is characterized in that concrete steps are: in 30mL pure water solvent, add template molecule tylosin tartrate, 0.15g carrier Styrene-divinylbenzene particles and functional monomers 2-acrylamido-2-methylpropanesulfonic acid and 1,4-butanediyl-3,3'-bis-1-vinylimidazole chloride, at 30 After 4 hours of pre-polymerization, the cross-linking agent N,N'-methylenebisacrylamide and the initiator azobisisobutyronitrile were added, wherein the molar ratio of template molecule, functional monomer, cross-linking agent and initiator was 1 : 6:15:0.12, then thermally initiate the polymerization reaction at 60 °C for 24 h, extract the template molecules with a methanol/acetic acid mixture with a volume ratio of 8-9:2-1 for 48 h to elute the template molecules, and rinse with methanol. The surface molecularly imprinted polymer of tylosin tartrate was obtained by vacuum drying at 60°C. 3. the application of the tylosin tartrate surface molecularly imprinted polymer obtained by the method described in any one of claims 1-2, it is characterized in that: this tylosin tartrate surface molecularly imprinted polymer has the The specific recognition performance of tylosin tartrate can be used to selectively adsorb trace amounts of tylosin tartrate in environmental samples.