Preparation method of environment-friendly spiramycin imprinted polymer

Abstract

The invention relates to the technical field of preparation of high-molecular compounds, and particularly discloses a preparation method of an environment-friendly spiramycin imprinted polymer, which comprises the following steps: step 1, by taking spiramycin (SPM) as a template molecule, hexamethylenediamine as a functional monomer and glutaraldehyde as a cross-linking agent, carrying out polymerization under the condition of not adding an initiator, so as to obtain a spiramycin imprinted polymer; the spiramycin imprinted polymer is obtained; and 2, after the spiramycin imprinted polymer is synthesized, firstly drying a product, and then grinding the product into particles by using a mortar. And the ground product is screened through a standard screen, and particles with the particle size range of 40-80 meshes are collected. And washing the screened particles for multiple times by using a 0.1 mol / L HCl solution, and monitoring the eluent by high performance liquid chromatography until the spiramycin signal completely disappears. And finally, drying the fully eluted material again to obtain the pure spiramycin imprinted polymer.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer compound preparation, and in particular relates to a method for preparing an environmentally friendly spiramycin imprinted polymer. Background Art

[0002] Molecular imprinting technology is an emerging material synthesis method with widespread applications in fields such as biosensors, drug delivery systems, and environmental monitoring. This technology embeds specific template molecules into polymer materials to form pores with highly selective recognition capabilities, enabling the effective capture and detection of target molecules. Molecularly imprinted polymers (MIPs) exhibit enormous potential for application in a variety of fields due to their specific recognition, strong practicality, superior mechanical properties, high stability, and reusability.

[0003] In traditional molecular imprinting techniques, organic solvents such as chloroform, acetonitrile, and toluene are key components of the synthesis process. These solvents, particularly in precipitation polymerization and suspension polymerization, act as pore-forming agents, crucial for preparing MIPs with uniform particle size and well-defined pore structures. However, the use of organic solvents poses a potential threat to the environment, making the development of environmentally friendly molecular imprinting polymer synthesis techniques particularly important.

[0004] On this basis, we proposed a method for preparing environmentally friendly spiramycin imprinted polymers. Glutaraldehyde was selected as an efficient cross-linking agent and 1,6-hexanediamine as a functional monomer. The amino groups in the hexanediamine molecule can form a stable template molecule-functional monomer complex with polar groups such as hydroxyl and carboxyl groups in the template molecule through intermolecular interactions, thereby enhancing the selective recognition ability of the polymer. Glutaraldehyde can react with active groups such as amino groups on the hexanediamine molecule to form a stable three-dimensional network polymer structure by forming covalent bonds, providing a solid support framework for MIPs. In order to verify the rationality of this method, spiramycin (SPM) was selected as the template molecule to synthesize spiramycin imprinted polymers (SPM-MIPs), and its adsorption performance was tested. Summary of the Invention

[0005] In view of this, the object of the present invention is to provide a method for preparing an environmentally friendly spiramycin imprinted polymer.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solution: a method for preparing an environmentally friendly spiramycin imprinted polymer, characterized in that it comprises the following steps:

[0007] Step 1: using spiramycin as a template molecule, hexamethylenediamine as a functional monomer, and glutaraldehyde as a cross-linking agent to obtain a spiramycin imprinted polymer;

[0008] In step 2, after the synthesis of the spiramycin imprinted polymer is completed, the product is first dried and then ground into granules using a mortar. The ground product is sieved through a standard sieve to collect particles with a particle size range of 40-80 mesh. The screened particles are then washed multiple times with 0.1 mol / L HCl solution, and the eluate is monitored by high-performance liquid chromatography until the spiramycin signal completely disappears. Finally, the fully eluted material is dried again to obtain a pure spiramycin imprinted polymer.

[0009] As a further embodiment of the present invention, in step 1, when the molar ratio of hexamethylenediamine and glutaraldehyde is the same, the molar ratio of spiramycin, hexamethylenediamine and glutaraldehyde is between 1:4:4 and 1:12:12, and the molar ratio of spiramycin, hexamethylenediamine and glutaraldehyde is 1:6:6, the adsorption amount and imprinting factor of the spiramycin imprinted polymer are greater than those of the spiramycin imprinted polymer prepared when the molar ratio of spiramycin, hexamethylenediamine and glutaraldehyde is 1:4:4, 1:8:8, 1:10:10, and 1:12:12.

[0010] As a further embodiment of the present invention, in step 1, when the molar ratio of hexamethylenediamine and glutaraldehyde is 1:6, the molar ratio of spiramycin, hexamethylenediamine and glutaraldehyde is between 1:6:4 and 1:6:8, and the molar ratio of spiramycin, hexamethylenediamine and glutaraldehyde is 1:6:6, the adsorption amount and imprinting factor of the spiramycin imprinted polymer are greater than those of the spiramycin imprinted polymer prepared when the molar ratio of spiramycin, hexamethylenediamine and glutaraldehyde is 1:6:4, 1:6:5, 1:6:7, and 1:6:8.

[0011] As a further embodiment of the present invention, in step 1, the polymerization reaction temperature is room temperature, and the polymerization reaction time is 2 hours.

[0012] As a further embodiment of the present invention, in step 2, spiramycin is detected using high performance liquid chromatography.

[0013] As a further embodiment of the present invention, in step 2, the HPLC detection conditions are as follows: chromatographic column: C18 (4.6 nm × 250 mm, 5 μm); mobile phase: acetonitrile / phosphate buffer (0.0167 M, pH = 6.5); volume ratio: 40:60; detection wavelength: 232 nm; column temperature: 40°C; flow rate: 1.0 mL / min.

[0014] As a further embodiment of the present invention, in step 1, polymerization is carried out without adding an initiator to obtain a polymer.

[0015] As a further optimization scheme of the present invention, in step 2, the following properties of the obtained spiramycin imprinted polymer are characterized:

[0016] (1) Morphological structure analysis: Scanning electron microscopy (SEM) was used to observe the surface morphology and microstructural characteristics of the polymer;

[0017] (2) Evaluation of adsorption performance: The saturated adsorption capacity of the polymer for spiramycin was determined by static adsorption experiments and compared with the adsorption performance of the non-imprinted polymer to verify the imprinting effect.

[0018] As a further approach to this invention, the ratio of spiramycin, hexamethylenediamine, and glutaraldehyde in step 1 affects the polymer's adsorption properties. Therefore, the effects of varying the molar ratio of these three components were investigated. A 1:6:6 molar ratio yielded the highest adsorption capacity and imprinting factor. To verify the performance of the SPM-MIP, a non-imprinted polymer (NIP) was also prepared using the same method as above, but without the template molecule SPM.

[0019] This invention proposes a method for preparing environmentally friendly spiramycin-imprinted polymers. As a further embodiment of the invention, glutaraldehyde is selected as a highly efficient crosslinker and 1,6-hexanediamine as a functional monomer. The amino groups in the hexanediamine molecule can react with polar groups such as hydroxyl and carboxyl groups in the template molecule through intermolecular interactions to form a stable template-functional monomer complex, thereby enhancing the polymer's selective recognition ability. Glutaraldehyde reacts with active groups such as amino groups on the hexanediamine molecule to form covalent bonds, constructing a stable three-dimensional network polymer structure, providing a solid support framework for the MIPs.

[0020] The beneficial effects of the present invention are as follows: a method for preparing an environmentally friendly spiramycin imprinted polymer is provided, wherein the spiramycin imprinted polymer is obtained by polymerization reaction using spiramycin as a template molecule, hexamethylenediamine as a functional monomer, and glutaraldehyde as a cross-linking agent. At the same time, among the spiramycin imprinted polymers obtained, an abnormal value (1:6:6) is obtained in the products with the best adsorption performance screened out. This preparation method can not only synthesize polymers under mild conditions, but also greatly improve the imprinting effect of the imprinted polymer. Since the initiator-free cross-linking polymerization is achieved in the aqueous phase, firstly, it is achieved in the aqueous phase, and secondly, there is no initiator, and the cross-linking polymerization is carried out without the participation of an organic solvent, therefore, this technical solution has the characteristics of being environmentally friendly and environmentally friendly; the SPM-MIP obtained by this technical solution has a high specific surface area and excellent selectivity, and can be widely used in the fields of biomedicine and environmental monitoring. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 The adsorption capacity of SPM-MIPs (NIPs) prepared from different proportions of SPM, hexamethylenediamine and glutaraldehyde provided by the present invention.

[0022] Figure 2The adsorption capacity of SPM-MIPs (NIPs) prepared with different proportions of SPM, hexamethylenediamine and glutaraldehyde provided by the present invention.

[0023] Figure 3 This is the SEM data of SPM-MIP (n-spiramycin: n-hexamethylenediamine: n-glutaraldehyde = 1:6:6) provided by the present invention. DETAILED DESCRIPTION

[0024] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the accompanying drawings. Obviously, the technical solutions described are only part of the present invention, not the entire invention. Based on the technical solutions of the present invention, all other technical solutions obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0025] Example 1

[0026] A method for preparing an environmentally friendly spiramycin imprinted polymer is characterized in that it comprises the following steps: step 1, using spiramycin as a template molecule, hexamethylenediamine as a functional monomer, and glutaraldehyde as a cross-linking agent to obtain a spiramycin imprinted polymer; step 2, after the synthesis of the spiramycin imprinted polymer is completed, first drying the product, and then grinding it into a granular state using a mortar. The ground product is sieved through a standard sieve to collect particles with a particle size range of 40-80 mesh. The screened particles are then washed multiple times with a 0.1 mol / L HCl solution, and the eluent is monitored by high performance liquid chromatography until the spiramycin signal completely disappears. Finally, the fully eluted material is dried again to obtain a pure spiramycin imprinted polymer.

[0027] Synthesis of Spiramycin-Imprinted Polymers: Spiramycin, hexamethylenediamine, and glutaraldehyde were mixed in specific molar ratios. The ratio of these three components affected the adsorption properties of the polymer. The specific ratios of the polymerization mixtures in the comparative examples are shown in Table 1. To verify the performance of the imprinted polymers, non-imprinted polymers (NIPs) were also prepared using the same method as above, except that no template molecules were added during the entire preparation process.

[0028] Table 1 Proportions of the polymerization reaction mixture

[0029]

[0030] Imprinting Effect Study: A 1 mg / mL SPM standard solution was prepared in 0.05 mol / L, pH 8, phosphate buffer. 25 mg of MIPs and NIPs were added to 5 mL of this solution at 37°C. The tubes containing these solutions were shaken at 120 rpm for 6 hours at room temperature. The remaining SPM concentration in each supernatant was determined by HPLC. Adsorption capacity Qe The calculation formula is:

[0031]

[0032] Where Q e (mg / g) is the adsorption amount of SPM-MIPs (NIPs) at adsorption equilibrium, C0 (mg / mL) is the initial adsorption concentration, C e (mg / mL) is the equilibrium adsorption concentration, V (mL) is the solution volume, and m (mg) is the mass of the polymer particles. The competitive binding ability of SPM-MIP can be calculated using the imprinting factor (IF) as follows:

[0033]

[0034] Among them, Q M is the binding ability of SPM on SPM-MIP, Q N is the binding ability of SPM on NIP.

[0035] according to Figure 1-Figure 2 It can be seen that based on the systematic component optimization study, when the molar ratio of SPM, hexamethylenediamine and glutaraldehyde changes in the range of 1:4:4 to 1:12:12, its adsorption performance shows a significant structure-activity relationship. Experimental data show that when the molar ratio of the three is 1:6:6, the molecularly imprinted polymers (MIPs) reach the maximum adsorption capacity (Q max =128.42 mg / g) and the optimal imprinting factor (IF=5.41). The stoichiometric ratio of SPM to hexamethylenediamine was further fixed at 1:6, and the mechanism of the effect of glutaraldehyde dosage on material properties was systematically investigated (e.g. Figure 2 As shown): As the glutaraldehyde ratio increases from 1:4 to 1:8, the adsorption amount of MIPs shows a nonlinear growth trend, which is attributed to the hierarchical pore structure formed by the increase in cross-linking degree. It is worth noting that the adsorption amount of non-imprinted polymers (NIPs) increases synchronously, indicating that excessive cross-linking will lead to an increase in the density of nonspecific sites, resulting in a marginal decreasing effect of the imprinting factor. Combined with the stoichiometric principle of the aldehyde-amine condensation reaction (amino group: aldehyde group = 1:1), the experiment determined that 1:6:6 is the optimal ratio, under which a dynamic balance between the construction of specific recognition sites and spatial stability is achieved. Subsequent structural characterization ( Figure 3 SEM images reveal structural characteristics) further verified the advantages of this ratio in three-dimensional network construction and provided a structural basis for the material's efficient molecular recognition performance.

[0036] The above description is merely a specific embodiment of the present application, but the scope of protection of the present application is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in this application should be included in the scope of protection of this application. Therefore, the scope of protection of this application should be based on the scope of protection of the claims.

[0037] Finally: The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing an environmentally friendly spiramycin imprinted polymer, characterized in that: The following steps are involved: Step 1: using spiramycin as a template molecule, hexamethylenediamine as a functional monomer, and glutaraldehyde as a cross-linking agent to obtain a spiramycin imprinted polymer; Step 2: After the synthesis of the spiramycin-imprinted polymer is completed, the product is first dried and then ground into granules using a mortar; the ground product is sieved through a standard sieve to collect particles with a particle size range of 40-80 mesh; the screened particles are then washed multiple times with 0.1 mol / L HCl solution, and the eluate is monitored by high-performance liquid chromatography until the spiramycin signal completely disappears; finally, the fully eluted material is dried again to obtain a pure spiramycin-imprinted polymer.

2. The method for preparing an environmentally friendly spiramycin imprinted polymer according to claim 1, characterized in that: In step 1, the molar ratio of spiramycin, hexamethylenediamine and glutaraldehyde is 1:6:

6.

3. The method for preparing an environmentally friendly spiramycin imprinted polymer according to claim 1, characterized in that: In step 1, the polymerization reaction temperature is room temperature, the polymerization reaction time is 12 hours, and the polymerization reaction pH is 7.

4.

4. The method for preparing an environmentally friendly spiramycin imprinted polymer according to claim 1, characterized in that: In step 2, the high performance liquid chromatography detection conditions are as follows: chromatographic column: C18, specifically 4.6 nm × 250 mm, 5 μm; mobile phase: acetonitrile / phosphate buffer, specifically 0.0167 M, pH = 6.5; volume ratio is 40:60; detection wavelength is 232 nm; column temperature: 40 ° C; flow rate: 1.0 mL / min.

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