Preparation method and application of rosinyl nitidine chloride molecularly imprinted polymer

Abstract

The invention belongs to the field of molecular imprinting, and particularly relates to a preparation method and application of a rosinyl nitidine chloride molecularly imprinted polymer. The invention discloses a rosin-based nitidine chloride molecularly imprinted polymer which is prepared by taking nitidine chloride as a template molecule, methacrylic acid as a functional monomer, ethylene glycol dimethacrylate and maleated rosin ethylene glycol acrylate as cross-linking agents, azodiisobutyronitrile as an initiator and methanol as a solvent. The rosin-based nitidine chloride molecularly imprinted polymer is prepared by adopting a precipitation polymerization method. The adsorption effect of the template molecule and different functional monomers on the nitidine chloride is discussed, and the result shows that the adsorption effect of the template molecule and the functional monomers on the nitidine chloride is optimal when the ratio of the template molecule to the functional monomers is 1: 6, the MIP is 5.91 mg / g, and the NIP is 1.22 mg / g. The preparation method disclosed by the invention is simple in process, has good adsorption performance and separation capacity on nitidine chloride, and has good specificity on selective adsorption of nitidine chloride.

Description

Technical Field

[0001] The invention belongs to the technical field of molecular imprinting, and in particular relates to a preparation method and application of a rosin-based nitidine chloride molecular imprinting polymer. Background Art

[0002] Nitidine chloride is a benzophenanthridine compound derived from the root of the traditional Chinese medicine Nitidine. It has a wide range of pharmacological activities in anti-inflammatory, analgesic and antioxidant aspects. At the same time, nitidine chloride is also the key component of Nitidine in exerting anti-tumor effects. Nitidine chloride is difficult to prepare and expensive, and an effective separation method is urgently needed.

[0003] Molecular imprinting method, also known as molecular imprinting technology, is a molecular imprinting polymer (Molecular Imprinting Technology, referred to as MIT) prepared by molecular imprinting technology. Molecular imprinting technology (MIT) is a method in which functional monomers self-assemble around template molecules and polymerize into three-dimensional cross-linked polymer materials in the presence of cross-linking agents. After removing the template molecules, the resulting polymer will form a cavity that can "memorize" the size, shape and functional group orientation of the template molecules. This polymer is a molecular imprinting polymer (MIP). Therefore, even in a complex mixture, MIP can recognize and rebind to the target molecule. MIP has the advantages of high selectivity, good stability, long service life, and wide application, and has been widely studied in the fields of materials and chemistry. Summary of the invention

[0004] The object of the present invention is to solve the above-mentioned problems and provide a preparation method and application of a rosin-based nitrile chloride molecularly imprinted polymer. The rosin-based nitrile chloride molecularly imprinted polymer is in the form of microspheres, has good adsorption performance and separation ability for nitrile chloride, and has good specificity for the selective adsorption of nitrile chloride.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] As a preferred technical solution, the precipitation polymerization method is specifically as follows: the template molecule nitrile chloride, the functional monomer methacrylic acid, the cross-linking agent ethylene glycol dimethacrylate and maleic rosin ethylene glycol acrylate, the initiator azobisisobutyronitrile and the solvent methanol are mixed to form a mixed solution, the mixed solution is shaken on a shaker to prepare a uniform light yellow mixed solution, after the polymerization reaction, the mixed solution is subjected to Soxhlet extraction and drying to obtain the rosin-based nitrile chloride molecular imprinting polymer.

[0007] As a preferred technical solution, the molar ratio of nitidine chloride to methacrylic acid in the mixed solution is 1:3, 1:4, 1:5, 1:6, or 1:7.

[0008] As a preferred technical solution, the molar ratio of nitidine chloride, ethylene glycol dimethacrylate and maleic rosin ethylene glycol acrylate in the mixed solution is 1:10:3.

[0009] As a preferred technical solution, the shaking time of the shaking table is 2 hours; and the drying time is 10-12 hours.

[0010] As a preferred technical solution, the polymerization reaction is carried out at 80°C for 6-12h.

[0011] As a preferred technical solution, the solvents for the Soxhlet extraction are methanol and glacial acetic acid, and the extraction time is 24-26 hours.

[0012] An application of the above-mentioned rosin-based nitrile chloride molecularly imprinted polymer, and an application of the rosin-based nitrile chloride molecularly imprinted polymer in the natural extraction of nitrile chloride.

[0013] As a preferred technical solution, the application is specifically as follows: adding rosin-based nitidine chloride molecular imprinting polymer to a mixed solution containing nitidine chloride, berberine hydrochloride and camptothecin, and adsorbing for 720 minutes at 30°C to extract nitidine chloride.

[0014] 1. The rosin-based nitrile chloride molecularly imprinted polymer of the present invention has an adsorption capacity of 2.18-5.91 mg / g, has good adsorption performance and separation ability for nitrile chloride, and has good specificity for the selective adsorption of nitrile chloride.

[0015] 2. The preparation method of the rosin-based nitrile chloride molecular imprinted polymer of the present invention is simple in process, convenient in operation and mild in conditions. The prepared rosin-based nitrile chloride molecular imprinted polymer has strong selective adsorption, strong anti-interference ability, good stability, fast adsorption rate and easy separation for the natural extraction of nitrile chloride, and is suitable for the natural extraction of nitrile chloride. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is the infrared spectrum of the rosin-based nitidine chloride molecularly imprinted polymer MIP prepared in Example 4 of the present invention

[0017] Figure 2 The infrared spectrum of the blank control group rosin-based non-chlorinated nitidine molecularly imprinted polymer NIP

[0018] Figure 3Figure 2 shows the adsorption amount of rosin-based nitidine chloride molecular imprinted polymers MIP with different molar ratios of nitidine chloride to methacrylic acid prepared in Examples 1, 2, 3, 4, and 5 of the present invention and rosin-based non-nitidine chloride molecular imprinted polymers NIP prepared in the blank control group.

[0019] Figure 4 The selectivity graph of the rosin-based nitidine chloride molecular imprinted polymer MIP prepared in Example 4 of the present invention and the rosin-based non-nitidine chloride molecular imprinted polymer NIP prepared in the blank control group is shown in FIG.

[0020] Figure 5 This is a SEM image of the rosin-based nitrile chloride molecularly imprinted polymer MIP prepared in Example 4 of the present invention.

[0021] Figure 6 SEM image of rosin-based non-chlorinated nitidine molecularly imprinted polymer NIP prepared as the blank control group

[0022] Figure 7 This is the TGA curve of the rosin-based nitidine chloride molecularly imprinted polymer MIP prepared in Example 4 of the present invention DETAILED DESCRIPTION

[0023] The present invention is further described in detail below by way of examples. These examples are only used to illustrate the present invention and do not limit the protection scope of the present invention.

[0024] Preparation of rosin-based nitidine chloride molecularly imprinted polymer:

[0025] Example 1

[0026] Step 1

[0027] Add 24 mg of nitidine chloride, 16 mg of methacrylic acid and 34 mL of methanol into a 250 mL three-necked flask and place it in a shaker for 2 h.

[0028] Step 2

[0029] Then, 0.12 g of ethylene glycol dimethacrylate, 0.17 g of maleated rosin ethylene glycol acrylate, and 45 mg of azobisisobutyronitrile were added, and the mixture was shaken on an ultrasonic cleaner for 15 minutes to prepare a uniform mixed solution. The treated mixed solution was placed in an oil bath at 80°C for reaction, with a stirring rate of 50 rpm and a reaction time of 8 hours to obtain a white polymer.

[0030] The polymer was filtered through a filter funnel, rinsed with methanol 2-3 times, wrapped with filter paper, and Soxhlet extracted with glacial acetic acid-methanol (1:9) for 24 hours. The polymer was dried for 24 hours and stored for later use to obtain rosin-based nitidine chloride molecular imprinting polymer (MIP).

[0031] The difference between the blank control group and Example 1 is that there is no template molecule nitidine chloride in the blank control group, and the other conditions are the same as those in Example 1 to prepare the rosin-based non-nitidine chloride molecular imprinting polymer NIP.

[0032] Example 2

[0033] Step 1

[0034] Add 24 mg of nitidine chloride, 21 mg of methacrylic acid and 34 mL of methanol into a 250 mL three-necked flask and place it in a shaker for 2 h.

[0035] Step 2

[0036] Then, 0.12 g of ethylene glycol dimethacrylate, 0.17 g of maleated rosin ethylene glycol acrylate, and 45 mg of azobisisobutyronitrile were added, and the mixture was shaken on an ultrasonic cleaner for 15 minutes to prepare a uniform mixed solution. The treated mixed solution was placed in an oil bath at 80°C for reaction, with a stirring rate of 50 rpm and a reaction time of 8 hours to obtain a white polymer.

[0037] The polymer was filtered through a filter funnel, rinsed with methanol 2-3 times, wrapped with filter paper, and Soxhlet extracted with glacial acetic acid-methanol (1:9) for 24 hours. The polymer was dried for 24 hours and stored for later use to obtain rosin-based nitidine chloride molecular imprinting polymer (MIP).

[0038] The difference between the blank control group and Example 2 is that there is no template molecule nitidine chloride in the blank control group, and the other conditions are the same as those in Example 2 to prepare the rosin-based non-nitidine chloride molecular imprinting polymer NIP.

[0039] Example 3

[0040] Step 1

[0041] Add 24 mg of nitidine chloride, 26 mg of methacrylic acid and 34 mL of methanol into a 250 mL three-necked flask and place it in a shaker for 2 h.

[0042] Step 2

[0043] Then, 0.12 g of ethylene glycol dimethacrylate, 0.17 g of maleated rosin ethylene glycol acrylate, and 45 mg of azobisisobutyronitrile were added, and the mixture was shaken on an ultrasonic cleaner for 15 minutes to prepare a uniform mixed solution. The treated mixed solution was placed in an oil bath at 80°C for reaction, with a stirring rate of 50 rpm and a reaction time of 8 hours to obtain a white polymer.

[0044] The polymer was filtered through a filter funnel, rinsed with methanol 2-3 times, wrapped with filter paper, and Soxhlet extracted with glacial acetic acid-methanol (1:9) for 24 hours. The polymer was dried for 24 hours and stored for later use to obtain rosin-based nitidine chloride molecular imprinting polymer (MIP).

[0045] The difference between the blank control group and Example 3 is that there is no template molecule nitidine chloride in the blank control group, and the other conditions are the same as those in Example 3 to prepare the rosin-based non-nitidine chloride molecular imprinting polymer NIP.

[0046] Example 4

[0047] Step 1

[0048] Add 24 mg of nitidine chloride, 31 mg of methacrylic acid and 34 mL of methanol into a 250 mL three-necked flask and place it in a shaker for 2 h.

[0049] Step 2

[0050] Then, 0.12 g of ethylene glycol dimethacrylate, 0.17 g of maleated rosin ethylene glycol acrylate, and 45 mg of azobisisobutyronitrile were added, and the mixture was shaken on an ultrasonic cleaner for 15 minutes to prepare a uniform mixed solution. The treated mixed solution was placed in an oil bath at 80°C for reaction, with a stirring rate of 50 rpm and a reaction time of 8 hours to obtain a white polymer.

[0051] The polymer was filtered through a filter funnel, rinsed with methanol 2-3 times, wrapped with filter paper, and Soxhlet extracted with glacial acetic acid-methanol (1:9) for 24 hours. The polymer was dried for 24 hours and stored for later use to obtain rosin-based nitidine chloride molecular imprinting polymer (MIP).

[0052] The difference between the blank control group and Example 4 is that there is no template molecule nitidine chloride in the blank control group, and the other conditions are the same as those in Example 4 to prepare the rosin-based non-nitidine chloride molecular imprinting polymer NIP.

[0053] Example 5

[0054] Step 1

[0055] Add 24 mg of nitidine chloride, 36 mg of methacrylic acid and 34 mL of methanol into a 250 mL three-necked flask and place it in a shaker for 2 h.

[0056] Step 2

[0057] Then, 0.12 g of ethylene glycol dimethacrylate, 0.17 g of maleated rosin ethylene glycol acrylate, and 45 mg of azobisisobutyronitrile were added, and the mixture was shaken on an ultrasonic cleaner for 15 minutes to prepare a uniform mixed solution. The treated mixed solution was placed in an oil bath at 80°C for reaction, with a stirring rate of 50 rpm and a reaction time of 8 hours to obtain a white polymer.

[0058] The polymer was filtered through a filter funnel, rinsed with methanol 2-3 times, wrapped with filter paper, and Soxhlet extracted with glacial acetic acid-methanol (1:9) for 24 hours. The polymer was dried for 24 hours and stored for later use to obtain rosin-based nitidine chloride molecular imprinting polymer (MIP).

[0059] The difference between the blank control group and Example 5 is that there is no template molecule nitidine chloride in the blank control group, and the other conditions are the same as those in Example 5, so as to prepare the rosin-based non-nitidine chloride molecular imprinting polymer NIP. Result analysis:

[0060] The rosin-based nitidine chloride molecular imprinted polymer MIP prepared in Example 4 of the present invention and the rosin-based nitidine chloride non-imprinted polymer NIP prepared in the blank control group were characterized and analyzed.

[0061] 1. After Fourier transform infrared spectroscopy detection, the results are as follows Figure 1 and 2 shown.

[0062] Figure 1 This is the infrared spectrum of the rosin-based nitidine chloride molecularly imprinted polymer MIP prepared in Example 4 of the present invention, Figure 2 This is the infrared spectrum of the blank control group rosin-based non-chlorinated nitidine molecular imprinting polymer NIP.

[0063] From the infrared spectra, we can see that the spectra of MIP and NIP are basically the same, indicating that the two polymers are the same substance, and the nitidine chloride in MIP has been completely eluted. -1 It is the -C=O stretching vibration peak. From the comparison of the two figures, it can be seen that the -COOH of the MAA part in MIP and the N + The electrostatic interaction between them caused the carbonyl bond to shorten, the density of the bonding electron cloud to increase, and the chemical bond force constant to increase, causing the absorption peak of -C=O to increase from 1728.31cm -1 The red shift is 1731.42 cm -1 This proves that the rosin-based nitidine chloride molecular imprinting polymer MIP was successfully prepared.

[0064] 2. After testing by thermogravimetric analyzer, the results are as follows Figure 7 shown.

[0065] Figure 7 This is the TGA curve of the rosin-based nitidine chloride molecularly imprinted polymer MIP prepared in Example 4 of the present invention.

[0066] The thermal stability of MIP was studied by TGA analysis, and the decomposition temperature of MIP was about 383 ° C, the maximum decomposition rate was about 425 ° C, and the final thermal decomposition temperature was about 448 ° C. The degradation was caused by the breakage of the crosslinker and the polymer backbone. The TGA results showed that MIP had good thermal stability.

[0067] Adsorption performance comparison

[0068] Take 10 mg of the rosin-based nitidine chloride molecular imprinted polymer MIP prepared in Examples 1, 2, 3, 4 and 5 of the present invention, add the MIP into a 10 mL nitidine chloride solution with a concentration of 40 g / L, oscillate at a rate of 150 r / min and a temperature of 30° C. The adsorption results of the MIP on nitidine chloride at different molar ratios of nitidine chloride to methacrylic acid are as follows: Figure 3 shown.

[0069] Take 10 mg of rosin-based non-chlorinated nitidine molecular imprinting polymer NIP prepared in the blank control group, add NIP into a 10 mL, 40 g / L chlorinated nitidine solution, oscillate at a rate of 150 r / min, and at a temperature of 30 ° C. The adsorption amount of NIP on chlorinated nitidine at different molar ratios of chlorinated nitidine and methacrylic acid is shown in the figure below. Figure 3 shown.

[0070] Figure 3 Graph showing the adsorption of nitidine chloride on the rosin-based nitidine chloride molecular imprinting polymers MIP prepared in Examples 1, 2, 3, 4 and 5 of the present invention and the rosin-based non-nitidine chloride molecular imprinting polymer NIP prepared in the blank control group at different molar ratios of nitidine chloride to methacrylic acid.

[0071] from Figure 3 It can be seen that among the rosin-based nitrile chloride molecular imprinted polymers MIP prepared in Examples 1, 2, 3, 4 and 5 of the present invention, the adsorption amount of nitrile chloride in Example 4 is the largest, which is 5.91 mg / g. The adsorption amount of the rosin-based non-nitrile chloride molecular imprinted polymer NIP prepared in the blank control group is 1.22 mg / g, and the imprinting factor is 4.84, which further proves that the imprinting is successful.

[0072] Application Example 4

[0073] Take 10 mg of the rosin-based nitidine chloride molecular imprinted polymer MIP prepared in Example 4 of the present invention, add the MIP to a mixed solution of nitidine chloride, berberine hydrochloride, and camptothecin at a concentration of 40 g / L, the volume of the mixed solution is 10 mL, the equilibrium time is 12 h, the oscillation speed is 150 r / min, the temperature is 30 ° C, and the selective adsorption results of MIP on nitidine chloride are as follows: Figure 4 shown.

[0074] Application Example 4

[0075] Take 10 mg of the rosin-based non-chlorinated nitidine molecular imprinting polymer NIP prepared in the blank control group, add NIP to a mixed solution of nitidine chloride, berberine hydrochloride, and camptothecin at a concentration of 40 g / L, the volume of the mixed solution is 10 mL, the equilibrium time is 12 h, the oscillation speed is 150 r / min, the temperature is 30 ° C, and the selective adsorption results of NIP on nitidine chloride are as follows Figure 4 shown.

[0076] Figure 4 This is a bar graph showing the selective adsorption of the rosin-based nitidine chloride molecular imprinted polymer MIP prepared in Example 4 of the present invention and the rosin-based non-nitidine chloride molecular imprinted polymer NIP prepared in the blank control group. Figure 4 It can be seen that in the mixed solution containing nitidine chloride, berberine hydrochloride and camptothecin, MIP showed strong selective adsorption, and its adsorption amount of nitidine chloride was greater than that of other substances. The adsorption amount of nitidine chloride by NIP was lower than that of MIP.

[0077] 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, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A rosin-based nitidine chloride molecularly imprinted polymer, characterized in that: The structural formula of the nitidine chloride is as follows:

2. The rosin-based nitidine chloride molecularly imprinted polymer according to claim 1, characterized in that: The adsorption capacity of the rosin-based nitidine chloride molecularly imprinted polymer is 2.18-5.91 mg / g.

3. A method for preparing a rosin-based nitidine chloride molecularly imprinted polymer according to claim 1 or 2, characterized in that: The preparation method comprises the following steps: using nitidine chloride as a template molecule, methacrylic acid as a functional monomer, ethylene glycol dimethacrylate and maleated rosin acrylate glycol ester as crosslinking agents, azobisisobutyronitrile as an initiator, and methanol as a solvent, and adopting a precipitation polymerization method to prepare a rosin-based nitidine chloride molecular imprinting polymer.

4. The method for preparing the rosin-based nitidine chloride molecularly imprinted polymer according to claim 3, characterized in that: The precipitation polymerization method specifically comprises the following steps: mixing a template molecule nitrile chloride, a functional monomer methacrylic acid, a cross-linking agent ethylene glycol dimethacrylate and maleated rosin ethylene glycol acrylate, an initiator azobisisobutyronitrile and a solvent methanol to form a mixed solution, shaking the mixed solution on a shaking table to prepare a uniform yellow mixed solution, and then subjecting the mixed solution to a polymerization reaction, Soxhlet extraction and drying to obtain the rosin-based nitrile chloride molecularly imprinted polymer.

5. The method for preparing the rosin-based nitidine chloride molecularly imprinted polymer according to claim 4, characterized in that: The molar ratio of nitidine chloride to methacrylic acid in the mixed solution is 1:3, 1:4, 1:5, 1:6, or 1:

7.

6. The method for preparing the rosin-based nitidine chloride molecularly imprinted polymer according to claim 4, characterized in that: The molar ratio of nitidine chloride, ethylene glycol dimethacrylate and maleic rosin ethylene glycol acrylate in the mixed solution is 1:10:

3.

7. The method for preparing the rosin-based nitidine chloride molecularly imprinted polymer according to claim 4, characterized in that: The shaking time of the shaking table is 1-2 hours; the drying time is 10-12 hours.

8. The method for preparing the rosin-based nitidine chloride molecularly imprinted polymer according to claim 4, characterized in that: The polymerization reaction is carried out at 50° C. for 12-14 hours and at 60-80° C. for 6-8 hours.

9. The method for preparing the rosin-based nitidine chloride molecularly imprinted polymer according to claim 4, characterized in that: The solvents for Soxhlet extraction are methanol and glacial acetic acid, and the extraction time is 23-26 hours.

10. An application of the rosin-based nitidine chloride molecularly imprinted polymer as claimed in claim 1 or 2, characterized in that: The invention discloses an application of the rosin-based nitidine chloride molecular imprinting polymer in the natural extraction of nitidine.

11. The use of the rosin-based nitidine chloride molecularly imprinted polymer according to claim 9, characterized in that: The application is specifically as follows: adding the rosin-based nitidine chloride molecular imprinting polymer into a mixed solution containing nitidine chloride, berberine hydrochloride and camptothecin, and adsorbing for 720 minutes at 30° C. to extract the nitidine chloride.

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