Preparation of amino-containing functional material and application of amino-containing functional material to separation of phenylethanoid glycoside compounds
By introducing amino and carboxylic functional groups into the porous carbon material, a secondary transport mechanism is formed, which solves the problem of low adsorption selectivity of porous carbon materials when adsorbing phenylethanol glycoside compounds, and achieves an efficient separation effect.
Patent Information
- Application Number
- CN202410824301.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-06-25
- Publication Date
- 2025-03-14
AI Technical Summary
When adsorbing phenylethanol glycoside compounds, the existing porous carbon materials have low adsorption selectivity, and the lack of specific surface functional groups leads to difficulty in identifying specific components of the target.
The kiwifruit structural porous carbon material (ACMC) is prepared through carbonization-etching-oxidation strategy, and amino and carboxy functional groups are introduced on the surface of the material to form secondary transport mechanisms such as molecular sieving and surface diffusion, reducing the transmission resistance of phenylethanol glycoside compounds.
The adsorption capacity and selectivity of porous carbon materials to phenylethanolamine compounds are significantly improved, and efficient separation effect is achieved.
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Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of porous carbon material preparation, and specifically relates to the preparation of an amino functional material and its use in separating phenylethanol glycoside compounds. Background Art
[0002] Cistanche tubulosa is a traditional edible and medicinal plant. It belongs to the parasitic plant of the Orobanchaceae family and is recorded in the Shennong Bencao as a tonic Chinese medicine. Due to its medicinal value, Cistanche tubulosa is widely used in traditional Chinese medicine preparations, functional food ingredients or food supplements. In order to ensure its safety, the China Food Safety Assessment Committee (CFSA) has passed the safety evaluation of Alxa Desert Cistanche in 2016, allowing Cistanche tubulosa to officially enter the food field. At present, the research on Cistanche tubulosa mainly focuses on extraction, separation and purification, and pharmacological effects. Researchers have found that the phenylethanoid glycosides it contains have pharmacological effects such as immunomodulatory effects, neuroprotective effects, antioxidant and anti-cancer effects, and hepatoprotective effects. In order to further study and exert its medicinal value, it is necessary to achieve efficient separation of phenylethanoid glycosides.
[0003] Porous carbon materials can be divided into three types according to the size of the pores: macroporous carbon, mesoporous carbon and microporous carbon. Porous carbon materials are widely used in the field of adsorption due to their adjustable pore structure, high porosity, high specific surface area, large pore volume and good stability. Studies have shown that compared with microporous carbon, mesoporous carbon prepared with phenolic resin (carbon source) has a higher adsorption capacity for chlorogenic acid. The reason is that the pore size of microporous carbon is small and chlorogenic acid cannot enter the pores. Mesoporous carbon has a high specific surface area and mesoporous structure, which can effectively adsorb chlorogenic acid. However, when porous carbon materials are used as adsorbents, their adsorption selectivity is often very low. The reason is that porous carbon materials lack specific surface functional groups after carbonization, so the specific recognition between them and the target components is low. Therefore, it is necessary to modify porous carbon materials in order to obtain porous carbon materials with better comprehensive performance.
[0004] The present invention provides a preparation method of an amino-containing functional material and its use in separating phenylethanol glycoside compounds. The kiwifruit structure porous carbon material (ACMC) has the advantages of both porous materials and multifunctional materials, and has easily adjustable porosity, rich carboxyl and amino groups, and outstanding physical and chemical properties. The present invention introduces sodium hydroxide to etch the carbon silicon material, and introduces hydrogen peroxide to graft the functional material, which can form secondary transport mechanisms such as molecular sieving and surface diffusion in the microspheres, construct a path for the rapid transmission of phenylethanol glycoside compounds, thereby reducing the transmission resistance of phenylethanol glycoside compounds into the functional material, improving the adsorption sites of phenylethanol glycoside compounds, and effectively improving the separation performance of the porous carbon material. A new and effective strategy is provided for the efficient separation of phenylethanol glycoside compounds. Summary of the invention
[0005] In view of the deficiencies in the prior art, the present invention provides a preparation method of an amino-containing functional material and its use in separating phenylethanol glycoside compounds. The present invention uses a carbonization-etching-oxidation strategy to make the material have the advantages of both porous materials and multifunctional materials, and has easily adjustable porosity, rich carboxyl and amino groups, and outstanding physical and chemical properties. The present invention introduces sodium hydroxide to etch the carbon silicon material and introduces hydrogen peroxide to graft the functional material, which can form secondary transport mechanisms such as molecular sieving and surface diffusion in the microspheres, construct a path for the rapid transmission of phenylethanol glycoside compounds, thereby reducing the transmission resistance of phenylethanol glycoside compounds, improving the adsorption sites of phenylethanol glycoside compounds, thereby effectively improving the separation performance of porous carbon materials, and has a good application in separating phenylethanol glycoside compounds under wet conditions.
[0006] The present invention also provides a method for preparing the above-mentioned amino-containing functional material, which specifically comprises the following steps:
[0007] (1) Anhydrous ethanol, ultrapure water and ammonia water were added to a 500 mL beaker, and the mixture was stirred to obtain a solution A. Then, ethylenediamine, 3-aminophenol, formaldehyde and tetraethoxysilane were added to the solution A to obtain a solution B, which was vigorously stirred, washed and dried to obtain a product P1.
[0008] (2) Under nitrogen protection, the obtained product P1 is placed in a tubular furnace for high-temperature calcination to obtain product C1.
[0009] (3) C1 is placed in a flask. Then, an alkaline solution is added to the flask, heated, and vigorously stirred to obtain solution C, which is washed and dried. The resulting product is added to a hydrogen peroxide solution, heated to obtain solution D, washed, and dried to obtain the target adsorbent.
[0010] Preferably, in step (1), the volume ratio of anhydrous ethanol to ultrapure water is 4:1.
[0011] Preferably, in step (1), the mass ratio of ethylenediamine, 3-aminophenol, formaldehyde and tetraethoxysilane is 7:16:35:70.
[0012] The ammonia water is added in an amount of 0.1 to 1 mol / L.
[0013] The drying temperature is 50-90° C. and the drying time is 12-36 hours.
[0014] Preferably, in step (2), the calcination temperature is 500-700° C. for 2-6 hours.
[0015] Preferably, in step (3), the concentration of the alkaline solution is 1 mol / L sodium hydroxide.
[0016] Preferably, in step (3), the heating temperature is 50 to 90° C. and the heating time is 3 to 10 hours.
[0017] The drying temperature is 50-90° C. and the drying time is 12-36 hours.
[0018] The detergents are ultrapure water and anhydrous ethanol.
[0019] Compared with the prior art, the present invention has the following beneficial effects:
[0020] Kiwifruit structure porous carbon adsorbent (ACMC) has the advantages of both porous materials and multifunctional materials, with easily adjustable porosity, rich carboxyl and amino groups and outstanding physical and chemical properties. The present invention introduces sodium hydroxide to etch the carbon silicon material, and introduces hydrogen peroxide to graft the functional material, which can form secondary transport mechanisms such as molecular sieving and surface diffusion in the microspheres, construct a path for the rapid transmission of phenylethanol glycoside compounds, thereby reducing the transmission resistance of phenylethanol glycoside compounds into the functional material, improving the adsorption sites of phenylethanol glycoside compounds, and effectively improving the separation performance of porous carbon materials.
[0021] The present invention obtains ACMC through a carbonization-etching-oxidation strategy. The inner and outer surfaces of ACMC have abundant carboxyl and amino groups, which enhance the adsorption affinity with phenylethanol glycoside compounds, accelerate the adsorption of phenylethanol glycoside compounds on the inner and outer surfaces, and thus improve the adsorption selectivity. These functional groups provide more adsorption sites, effectively increase the interaction force between phenylethanol glycoside compounds and ACMC, and make the adsorption more firm and stable. Test results show that the adsorption capacity and selectivity of the amino-containing functional material ACMC for phenylethanol glycoside compounds are 201.49 mg / g and 5.74, respectively. A new and effective strategy is provided for the efficient separation of phenylethanol glycoside compounds. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Figure 1 This is a transmission electron microscopy image of the amino-containing functional material ACMC-1 prepared in Example 1.
[0023] Figure 2 This is a transmission electron microscopy image of the amino-containing functional material ACMC-2 prepared in Example 2.
[0024] Figure 3 This is a transmission electron microscopy image of the amino-containing functional material ACMC-3 prepared in Example 3.
[0025] Figure 4 This is a transmission electron micrograph of the amino-containing functional material ACMC-4 prepared in Example 4.
[0026] Figure 5This is a transmission electron micrograph of the amino-containing functional material ACMC-5 prepared in Example 5.
[0027] Figure 6 This is a transmission electron microscope image of the functional material MC prepared in Comparative Example 1. DETAILED DESCRIPTION
[0028] The present invention is further described below in conjunction with the accompanying drawings and specific embodiments, but the protection scope of the present invention is not limited thereto.
[0029] Embodiment 1:
[0030] (1) Take a beaker with a capacity of 500 mL, pour 240 mL of anhydrous ethanol, 60 mL of ultrapure water and ammonia water into the beaker in sequence. Ultrasound is used to make them completely and evenly mixed. Next, 1.05 g of ethylenediamine and 2.4 g of 3-aminophenol, 2.7 g of formaldehyde and 10.8 g of tetraethoxysilane are added to the mixed solution respectively, and stirring is continued for 3 h. After the reaction is completed, the reaction solution is washed to neutrality, and then the washed product is vacuum dried for 12 h to obtain product P1.
[0031] (2) Weigh 3 g of substance P1 and place it in a tube furnace for calcination. Start heating from room temperature until the temperature reaches 500°C and maintain for 4 hours. Ensure uniformity and stability during the heating process. In order to protect the stability of the substance during the calcination process, nitrogen needs to be introduced to provide protection. After the calcination is completed, product C1 is obtained.
[0032] (3) Take out 1g of C1 substance and put it into a 500mL flask. Slowly add 2.0mol / L sodium hydroxide solution. Stir and heat to a constant temperature of 75℃ for 10h. After the reaction is completed, the product is washed and then dried by vacuum drying at 50℃ for 12h. The dried product is added to a hydrogen peroxide solution and reacted at a constant temperature of 60℃ for 3h. After the reaction time, the product is washed to separate and purify. Finally, the product is dried again by vacuum drying at 50℃ for 12h to obtain ACMC-1.
[0033] The transmission electron microscope image of the amino functional material ACMC-1 is as follows Figure 1 As shown, from Figure 1 It can be seen that the amino-containing functional material has good radioactive pores and the microsphere diameter is 270nm.
[0034] In this example, the amino-functional material ACMC-1 was tested for adsorption and separation of crude extracts of phenylethanoid glycosides under wet conditions at 30°C and 150 r / min. The test results showed that the adsorption capacity and selectivity of the amino-functional material ACMC-1 for phenylethanoid glycosides were 196.49 mg / g and 2.93, respectively.
[0035] Embodiment 2:
[0036] In this embodiment, the amino functional material ACMC-2 is prepared by the method described in Embodiment 1, with the following differences: in step (1), the addition ratio of formaldehyde to tetraethoxysilane is 1:3, that is, the formaldehyde weighed in step (1) is changed from 2.7 g to 3.6 g; in step (2), calcination at 500°C for 2 h is changed to calcination at 700°C for 2 h; in step (3), the concentration of the sodium hydroxide solution is changed from 2 mol / L to 4 mol / L; in step (3), magnetic stirring at 75°C for 10 h is changed to 80°C for 10 h; in step (3), vacuum drying at 50°C for 12 h to remove the solvent is changed to vacuum drying at 90°C for 24 h to remove the solvent.
[0037] The transmission electron microscope image of the amino functional material ACMC-2 is as follows Figure 2 As shown, from Figure 2 It can be seen that the amino-functional material has good radioactive pores, but the size of the microspheres is uneven, distributed in the range of 180 to 240 nm.
[0038] In this example, the amino functional material ACMC-2 was tested for adsorption and separation of crude extract of phenylethanoid glycosides under wet conditions at 30°C and 150 r / min. The test results showed that the adsorption capacity and selectivity of the amino functional material ACMC-2 for phenylethanoid glycosides were 211.29 mg / g and 3.74, respectively.
[0039] Embodiment 3:
[0040] In this embodiment, the amino functional material ACMC-3 is prepared by the method described in Embodiment 1, with the following differences: in step (1), the addition ratio of formaldehyde to tetraethoxysilane is 1:2, that is, in step (1), 2.7 g of formaldehyde is changed to 5.4 g; in step (2), calcination at 500°C for 2 h is changed to calcination at 550°C for 2 h; in step (3), the concentration of the sodium hydroxide solution is changed from 2 mol / L to 1 mol / L; in step (3), magnetic stirring at 75°C for 10 h is changed to 85°C for 10 h; in step (3), vacuum drying at 50°C for 12 h to remove the solvent is changed to vacuum drying at 60°C for 12 h to remove the solvent.
[0041] The transmission electron microscope image of the amino functional material ACMC-3 is as follows Figure 3 As shown, from Figure 3 It can be seen that the amino-containing functional material has good radioactive pores and the microsphere diameter is 230nm.
[0042] In this example, the amino-functional material ACMC-3 was tested for adsorption and separation of crude extracts of phenylethanoid glycosides under wet conditions at 30°C and 150 r / min. The test results showed that the adsorption capacity and selectivity of the amino-functional material ACMC-3 for phenylethanoid glycosides were 201.49 mg / g and 5.74, respectively.
[0043] Embodiment 4:
[0044] In this example, the amino functional material ACMC-4 was prepared by the method described in Example 1, with the following differences: in step (1), the addition ratio of formaldehyde to tetraethoxysilane was 2:1, that is, the formaldehyde weighed in step (1) was changed from 2.7 g to 21.6 g; in step (2), calcination at 500°C for 2 h was changed to calcination at 600°C for 3 h; in step (3), the concentration of the sodium hydroxide solution was changed from 2 mol / L to 0.5 mol / L; in step (3), magnetic stirring at 75°C for 10 h was changed to 85°C for 15 h; in step (3), vacuum drying at 50°C for 12 h to remove the solvent was changed to vacuum drying at 80°C for 24 h to remove the solvent.
[0045] The transmission electron microscope image of the amino functional material ACMC-4 is as follows Figure 4 As shown, from Figure 4 It can be seen that part of the pores of the amino-functional material collapsed, resulting in the blockage of some pores, and the diameter of the microspheres was 230 nm.
[0046] In this example, the amino functional material ACMC-4 was tested for adsorption and separation of crude extracts of phenylethanol glycosides under wet conditions at 30°C and 150 r / min. The test results showed that the adsorption capacity and selectivity of the amino functional material ACMC-4 for phenylethanol glycosides were 121.43 mg / g and 6.74, respectively.
[0047] Embodiment 5:
[0048] In this embodiment, the amino functional material ACMC-5 is prepared by the method described in Embodiment 1, with the following differences: in step (1), the addition ratio of formaldehyde to tetraethoxysilane is 1:1, that is, in step (1), the formaldehyde weighed in an amount of 2.7 g is changed to 10.8 g; in step (2), calcination at 500°C for 2 h is changed to calcination at 600°C for 2 h; in step (3), the concentration of the sodium hydroxide solution is changed from 2 mol / L to 0.5 mol / L; in step (3), magnetic stirring at 75°C for 10 h is changed to 85°C for 20 h; in step (3), vacuum drying at 50°C for 12 h to remove the solvent is changed to vacuum drying at 60°C for 24 h to remove the solvent.
[0049] The transmission electron microscope image of the amino functional material ACMC-5 is as follows Figure 5 As shown, from Figure 5 It can be seen that the amino-containing functional material has good radioactive pores and the microsphere diameter is 250nm.
[0050] In this example, the amino functional material ACMC-5 was tested for adsorption and separation of crude extract of phenylethanol glycosides under wet conditions at 30°C and 150 r / min. The test results showed that the adsorption capacity and selectivity of the amino functional material ACMC-5 for phenylethanol glycosides were 205.19 mg / g and 4.14, respectively.
[0051] Comparative Example 1:
[0052] In this comparative example, a functional material MC was prepared, and the preparation method of the functional material MC is as follows:
[0053] Take a beaker with a capacity of 500mL, pour 240mL of anhydrous ethanol, 60mL of ultrapure water and ammonia water into the beaker in turn. Ultrasound is used to make it completely and evenly mixed. Next, 1.05g of ethylenediamine and 2.4g of 3-aminophenol, 2.7g of formaldehyde and 10.8g of tetraethoxysilane are added to the mixed solution respectively, and stirring is continued for 5h. After the reaction is completed, the reaction solution is washed to neutrality, and then the washed product is vacuum dried for 12h to obtain the product MC.
[0054] The transmission electron microscope image of the amino functional material MC is as follows Figure 6 As shown, from Figure 6 It can be seen that the amino-containing functional material is spherical with almost no pores, and the diameter of the microsphere is 260nm.
[0055] In this example, the amino-functional material MC was tested for adsorption and separation of phenylethanoid glycosides crude extract under wet conditions at 30°C and 150 r / min. The test results showed that the adsorption capacity and selectivity of the amino-functional material MC for phenylethanoid glycosides were 35.58 mg / g and 2.13, respectively.
[0056] In summary, the amino-containing functional material of the present invention combines the advantages of porous materials and multifunctional materials to form an amino porous transfer path in the microspheres, and utilizes the porous structure to reduce the mass transfer resistance, which is beneficial to the penetration of phenylethanol glycoside compounds. In addition, ACMC is rich in carboxyl and amino groups, which is beneficial to the enhancement of the promotion transfer mechanism in the microspheres and to improve the selectivity of phenylethanol glycoside compounds.
[0057] The amino functional material of the present invention has good separation performance of phenylethanoid glycoside compounds, a simple preparation process, controllable reaction, cheap and easy-to-obtain raw materials, mild conditions, and good industrial application value. The embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments. Without departing from the essential content of the present invention, any obvious improvements, substitutions or modifications that can be made by those skilled in the art belong to the protection scope of the present invention.
Claims
1. An amino-functional material for separating phenylethanol glycoside compounds, characterized in that: The preparation method comprises the following steps: (1) Anhydrous ethanol, ultrapure water and ammonia water were added to a beaker with a capacity of 250 mL, and mixed and stirred to obtain solution A. Then, ethylenediamine, 3-aminophenol, formaldehyde and tetraethoxysilane were added to solution A to obtain solution B, which was vigorously stirred, and the product was washed and dried to obtain product P1. (2) Under nitrogen protection, the obtained product P1 is placed in a tubular furnace for high-temperature calcination to obtain product C1. (3) C1 is placed in a flask, and then an alkaline solution is added to the flask, heated, and vigorously stirred to obtain solution C, which is washed and dried. The obtained product is added to a hydrogen peroxide solution, heated to obtain solution D, and the product is washed and dried to obtain the target adsorbent.
2. The method for preparing the amino-containing functional material according to claim 1, characterized in that: In step (1), the mass ratio of formaldehyde to tetraethoxysilane is 7:16:36:
70.
3. The method for preparing the amino-containing functional material according to claim 1, characterized in that: In step (1), the concentration of the aqueous ammonia is 0.1 to 1 mol / L.
4. The method for preparing the amino-containing functional material according to claim 1, characterized in that: In step (1), the drying conditions are: vacuum drying at 50-90° C. for 12-36 hours.
5. The method for preparing the amino-containing functional material according to claim 1, characterized in that: In step (2), the calcination conditions are: high temperature calcination at 500-700° C. for 2-12 hours.
6. The method for preparing the amino-containing functional material according to claim 1, characterized in that: In step (3), the concentration of the alkaline solution is 1 mol / L sodium hydroxide. The heating temperature is 50 to 90° C. and the heating time is 3 to 10 hours.
7. The method for preparing the amino-containing functional material according to claim 1, characterized in that: In step (3), the concentration of hydrogen peroxide is 20-31%.
8. The method for preparing the amino-containing functional material according to claim 1, characterized in that: In step (3), the drying conditions are: vacuum drying at 50-90° C. for 12-36 hours.
9. Use of the amino-containing functional material according to claim 1 in separating phenylethanol glycoside compounds.
10. The use according to claim 9, characterized in that: The phenylethanol glycoside compound is a phenylethanol glycoside compound under wet conditions.