Preparation of polyion liquid functionalized MXene and application of polyion liquid functionalized MXene in separation and purification of active ingredients of cistanche deserticola

Abstract

The invention provides preparation of polyion liquid functionalized MXene and application of the polyion liquid functionalized MXene in separation and purification of active ingredients of cistanche deserticola, and belongs to the technical field of preparation of polyion liquid, two-dimensional materials and composite materials. The polyion liquid-MXene composite material is prepared on the basis of host-guest interaction between polyion liquid and MXene. The material has a three-dimensional cross-linked hierarchical porous structure, and the three-dimensional cross-linked hierarchical porous structure can provide an open and rapid transmission channel. The material has a good effect on separation and purification of active ingredients of cistanche, and the polyion liquid functionalized MXene natural product separation and purification material and the preparation method thereof are simple, wide in practicability and excellent in separation and purification performance. A new effective strategy is provided for efficiently separating and purifying the active ingredients of the cistanche deserticola.

Description

Technical Field

[0001] The present invention belongs to the technical field of preparation of polyionic liquids, two-dimensional materials and composite materials, and specifically relates to the preparation of a polyionic liquid-MXene composite material with a three-dimensional cross-linked hierarchical porous structure and the use of the polyionic liquid-MXene composite material for separating active ingredients of Cistanche deserticola. Background Art

[0002] As a traditional Chinese medicinal material, Cistanche deserticola has attracted widespread attention in many industries in recent years, especially in the fields of medicine, health products and food industry. It has gradually become a multifunctional natural plant resource due to its unique pharmacological effects and bioactive ingredients. In the field of medicine, Cistanche deserticola has antioxidant, anti-fatigue, and immune-enhancing effects, which makes it have broad application prospects in modern medicine. At the same time, as a natural herbal ingredient, Cistanche deserticola has gradually become an important raw material in many health products, especially in enhancing physical strength and regulating the immune system. In addition, it is also used as a health supplement for some special populations, such as the elderly and manual laborers, which helps to relieve fatigue and delay aging. In order to further study and exert its medicinal value, it is necessary to separate and purify the active ingredients of Cistanche deserticola.

[0003] As a green solvent, ionic liquids have shown great potential in the extraction and separation of bioactive ingredients due to their high adjustability and good solubility. Compared with traditional organic solvents or inorganic adsorbents, ionic liquids not only have higher solubility and stronger thermal stability, but also have adjustable polarity and surface activity, making them an ideal choice for the extraction and purification of bioactive ingredients. MXene has the characteristics of adjustable surface functional groups and large interlayer spacing. And its unique structure and surface properties make it a carrier that can effectively carry other functional materials, thereby constructing a composite adsorbent with specific properties.

[0004] The present invention provides a preparation method of a polyionic liquid-MXene composite material and its use in separating active ingredients of Cistanche deserticola. The polyionic liquid-MXene composite material has a three-dimensional cross-linked hierarchical porous structure. The polyionic liquid-MXene of the three-dimensional cross-linked hierarchical porous structure can provide an open and fast transmission channel. A path for rapid transmission of active ingredients of Cistanche deserticola is constructed, thereby reducing the transmission resistance of active ingredients of Cistanche deserticola into functional materials, improving the adsorption sites of active ingredients of Cistanche deserticola, and effectively improving the separation performance of the polyionic liquid-MXene composite material. A new and effective strategy is provided for efficiently separating active ingredients of Cistanche deserticola. Summary of the invention

[0005] In view of the deficiencies in the prior art, the present invention provides a preparation of a polyionic liquid-MXene composite material and its use in separating the active ingredients of Cistanche deserticola. The present invention prepares a polyionic liquid-MXene composite material based on hydrogen bonds, electrostatic and other interaction forces between polyionic liquid and MXene. The composite material has a three-dimensional cross-linked hierarchical porous structure, and the polyionic liquid-MXene of the three-dimensional cross-linked hierarchical porous structure can provide an open and fast transmission channel. A path for the rapid transmission of the active ingredients of Cistanche deserticola is constructed, thereby reducing the transmission resistance of the active ingredients of Cistanche deserticola and improving the adsorption sites of the active ingredients of Cistanche deserticola. The material has a good effect on the separation and purification of the active ingredients of Cistanche deserticola. This natural product separation and purification material of polyionic liquid functionalized MXene and its preparation method are simple, widely practical, and have excellent separation and purification performance.

[0006] The present invention also provides a method for preparing the above-mentioned polyionic liquid-MXene composite material, which specifically comprises the following steps:

[0007] (1) Titanium aluminum carbide and hydrofluoric acid are added to a 200 mL polytetrafluoroethylene container to obtain a mixture A, and then the mixture A is evenly dispersed and heated and stirred. After the reaction is completed, a viscous black substance B is formed. Then, the product B is washed to neutrality and dried to obtain a product P1.

[0008] (2) 1-vinylimidazole, chloroform and 1,2-dibromoethane are uniformly dispersed to obtain a mixture C, and the mixture C is heated and stirred under reflux under nitrogen protection. After the reaction is completed, a precipitate D is obtained, the precipitate D is washed, and then the substance D is obtained by rotary evaporation to obtain a product ionic liquid P2.

[0009] (3) P1, P2, ultrapure water, ethanol, butylene glycol and azobisisobutyronitrile are placed in a flask, dispersed evenly, heated and stirred to obtain a precipitate E. Finally, the precipitate E is washed and dried overnight to obtain the target composite material.

[0010] Preferably, in step (1), the mass ratio of titanium aluminum carbide to hydrofluoric acid is 1:10-20.

[0011] The reaction conditions are 20-50° C. for 24-72 hours.

[0012] The drying condition is drying at 50-100° C. for 5-48 hours.

[0013] Preferably, in step (2), the amount of 1-vinylimidazole, chloroform and 1,2-dibromoethane is in the following relationship: 1-10 mmol; 5-30 mmol; 1-5 mmol.

[0014] The reaction conditions are 50-130°C for 6-36 hours.

[0015] Preferably, in step (3), the dosage ratio of P1, P2, ultrapure water, ethanol, butylene glycol and azobisisobutyronitrile is: 0.1-0.5 g; 0.1-0.5 g; 0.3-2.0 g; 0.3-2.0 g; 0.01-0.5 g; 0.01-0.5 g.

[0016] The reaction conditions are 50-130° C. for 6-36 hours.

[0017] The drying condition is drying at 50-100° C. for 6-48 hours.

[0018] Preferably, in step (3), the heating temperature is 50 to 90° C. and the heating time is 3 to 10 hours.

[0019] The drying temperature is 50-90° C. and the drying time is 12-36 hours.

[0020] The ultrasonic dispersion time is 0.5 to 3 hours.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] The polyionic liquid-MXene composite adsorbent has the advantages of both porous materials and multifunctional materials, and has easily adjustable porosity, rich hydroxyl groups and outstanding physical and chemical properties. The present invention introduces polyionic liquid to functionalize MXene, and introduces butenediol to graft the composite material, which can form a three-dimensional cross-linked hierarchical porous structure in the composite material, construct a path for the rapid transmission of the active ingredients of Cistanche deserticola, thereby reducing the transmission resistance of the active ingredients of Cistanche deserticola into the functional material, improving the adsorption sites of the active ingredients of Cistanche deserticola, and effectively improving the separation performance of the polyionic liquid-MXene composite material.

[0023] The present invention combines the advantages of polyionic liquid and MXene to achieve a synergistic effect. The inner and outer surfaces of the polyionic liquid-MXene composite material are rich in hydroxyl groups, which enhances the adsorption affinity with the active ingredients of Cistanche deserticola, accelerates the adsorption of the active ingredients of Cistanche deserticola on the inner and outer surfaces, and thus improves the adsorption selectivity. The preparation process of the composite material is simple, the reaction is controllable, the raw materials are cheap and readily available, and the conditions are mild, which can promote the complementary advantages of ionic liquids and MXene. The test results show that the adsorption capacity and selectivity of the polyionic liquid-MXene composite material for the active ingredients of Cistanche deserticola are 358.49 mg / g and 2.94, respectively. A new and effective strategy is provided for the efficient separation of the active ingredients of Cistanche deserticola. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is a scanning electron microscope image of the polyionic liquid-MXene composite material prepared in Example 1.

[0025] Figure 2 This is a transmission electron microscopy image of the polyionic liquid-MXene composite material prepared in Example 1.

[0026] Figure 3 This is a scanning electron microscope image of the composite material MI prepared in Comparative Example 1.

[0027] Figure 4 This is a transmission electron microscope image of the composite material MI 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) 1 g of titanium aluminum carbide and 10 g of hydrofluoric acid were added to a 200 mL polytetrafluoroethylene container, and the mixture was stirred to obtain a solution A. The mixture was stirred and reacted at 30° C. for 48 h. After the reaction was completed, a viscous black substance B was obtained. Subsequently, the black substance B was washed until it was neutral and dried to obtain a product P1.

[0031] (2) 0.4 g of 1-vinyl imidazole, 2.5 g of chloroform and 0.4 g of 1,2-dibromoethane were mixed and dispersed uniformly by ultrasonication to obtain a mixture C. The mixture C was heated at 50° C. and stirred under reflux for 30 h under nitrogen protection. After the reaction, a substance D was obtained. The substance D was washed and then rotary evaporated to obtain a product ionic liquid P2.

[0032] (3) 0.1 g P1, 0.15 g P2, 0.6 g ultrapure water, 0.6 g ethanol, 0.03 g butene glycol and 0.02 g azobisisobutyronitrile were placed in a flask, ultrasonicated for 0.5 h to make it uniformly dispersed, and heated at 50 ° C and stirred for 36 h under nitrogen protection. After the reaction, substance E was obtained. Finally, the mixture E was washed and dried overnight to obtain the target polyionic liquid-MXene composite material.

[0033] The scanning electron microscope image of the polyionic liquid-MXene composite material is as follows Figure 1 And transmission electron microscopy images Figure 2 As shown, it can be seen from the SEM image that the ionic liquid is evenly distributed on the surface of the polyionic liquid-MXene composite material, and it can be seen from the TEM image that the polyionic liquid-MXene composite material still retains a certain size of interlayer spacing.

[0034] In this example, the adsorption, separation and purification test of the crude extract of the active ingredients of Cistanche deserticola by the polyionic liquid-MXene composite material was also investigated at 30°C and 150 r / min. The test results showed that the adsorption capacity and selectivity of the polyionic liquid-MXene composite material for the active ingredients of Cistanche deserticola were 265.20 mg / g and 3.13, respectively.

[0035] Embodiment 2:

[0036] In this embodiment, the method described in Embodiment 1 was used to prepare a polyionic liquid-MXene composite material, with the following differences: in step (1), 10 g of hydrofluoric acid was weighed instead of 20 g, and the reaction was stirred at 30°C instead of 50°C; in step (2), 2.5 g of chloroform was weighed instead of 1.6 g, and heating at 50°C and stirring for 36 h under nitrogen protection was changed to heating at 80°C and stirring under reflux for 12 h; in step (3), 0.03 g of butene glycol was weighed instead of 0.06 g, and heating at 50°C and stirring for 36 h under nitrogen protection was changed to heating at 80°C and stirring for 12 h.

[0037] In this example, the polyionic liquid-MXene composite material was tested for adsorption and separation of the crude extract of the active ingredients of Cistanche deserticola at 30°C and 150 r / min. The test results showed that the adsorption capacity and selectivity of the polyionic liquid-MXene composite material for the active ingredients of Cistanche deserticola were 354.20 mg / g and 2.89, respectively.

[0038] Embodiment 3:

[0039] In this embodiment, the method described in Embodiment 1 was used to prepare the polyionic liquid-MXene composite material, with the following differences: in step (1), the reaction time of 48 h was changed to 36 h; in step (2), 0.4 g of 1,2-dibromoethane was changed to 0.8 g of 1,2-dibromoethane, and heating at 50° C. and stirring for 36 h under nitrogen protection was changed to heating at 130° C. and stirring under reflux for 6 h; in step (3), 0.15 g of P2 was changed to 0.3 g of P2, and 0.02 g of azobisisobutyronitrile was changed to 0.2 g of azobisisobutyronitrile.

[0040] In this example, the polyionic liquid-MXene composite material was tested for adsorption and separation of the crude extract of the active ingredients of Cistanche deserticola at 30°C and 150 r / min. The test results showed that the adsorption capacity and selectivity of the polyionic liquid-MXene composite material for the active ingredients of Cistanche deserticola were 251.49 mg / g and 2.74, respectively.

[0041] Embodiment 4:

[0042] In this embodiment, the method described in Embodiment 1 was used to prepare the polyionic liquid-MXene composite material, with the following differences: in step (1), the reaction time of 48 h was changed to 24 h; in step (2), 2.5 g of chloroform was changed to 3.0 g of chloroform, 0.4 g of 1,2-dibromoethane was changed to 0.3 g of 1,2-dibromoethane, and heating at 50 ° C and stirring for 36 h under nitrogen protection was changed to heating at 110 ° C and stirring and refluxing for 8 h; in step (3), 0.15 g of P2 was changed to 0.5 g of P2, 0.6 g of ethanol was changed to 1.6 g of ethanol, 0.03 g of butene glycol was changed to 0.3 g of butene glycol, and heating at 50 ° C and stirring for 36 h under nitrogen protection was changed to heating at 60 ° C and stirring for 24 h under nitrogen protection.

[0043] In this example, the adsorption and separation test of the crude extract of the active ingredients of Cistanche deserticola by the polyionic liquid-MXene composite material was also investigated at 30°C and 150 r / min. The test results showed that the adsorption capacity and selectivity of the polyionic liquid-MXene composite material for the active ingredients of Cistanche deserticola were 221.43 mg / g and 2.61, respectively.

[0044] Embodiment 5:

[0045] In this embodiment, the method described in Embodiment 1 is adopted to prepare the polyionic liquid-MXene composite material, with the following differences: in step (1), the reaction time of 48 h is changed to 72 h; in step (2), the weighing of 0.4 g 1-vinylimidazole is changed to 0.8 g 1-vinylimidazole, the weighing of 2.5 g chloroform is changed to 0.8 g chloroform, and the heating at 50°C and stirring for 36 h under nitrogen protection is changed to heating at 130°C and stirring and refluxing for 24 h; in step (3), the weighing of 0.1 g P1 is changed to 0.3 g P1, the weighing of 0.6 g ethanol is changed to 2.0 g ethanol, the weighing of 0.03 g butene glycol is changed to 0.5 g butene glycol, the weighing of 0.02 g azobisisobutyronitrile is changed to 0.5 g azobisisobutyronitrile, and the heating at 50°C and stirring for 36 h under nitrogen protection is changed to heating at 100°C and stirring for 10 h under nitrogen protection.

[0046] In this example, the adsorption and separation test of the crude extract of the active ingredients of Cistanche deserticola by the polyionic liquid-MXene composite material was also investigated at 30°C and 150 r / min. The test results showed that the adsorption capacity and selectivity of the polyionic liquid-MXene composite material for the active ingredients of Cistanche deserticola were 205.69 mg / g and 2.14, respectively.

[0047] Comparative Example 1:

[0048] In this comparative example, a composite material MI is prepared, and the preparation method of the functional material MI is as follows:

[0049] 0.1g P1, 0.15g P2, 0.3g ultrapure water, 0.3g ethanol, 0.07g ethylene glycol dimethacrylate and 0.02g azobisisobutyronitrile were placed in a flask, ultrasonicated for 0.5h to make it evenly dispersed, heated at 80°C and stirred for 18h under nitrogen protection. After the reaction, substance E was obtained. Finally, mixture E was washed and dried overnight to obtain the target composite material MI.

[0050] The scanning electron microscope image of the composite material MI is as follows Figure 3 And transmission electron microscopy images Figure 4 As shown in the figure, SEM shows that the composite MI does not have a regular appearance. Figure 3 No clear interlayer spacing can be seen in TEM.

[0051] In this example, the composite material MI was also tested for adsorption, separation and purification of the crude extract of the active ingredients of Cistanche deserticola at 30°C and 150 r / min. The test results showed that the adsorption capacity and selectivity of the composite material MI for the active ingredients of Cistanche deserticola were 165.58 mg / g and 2.13, respectively.

[0052] In summary, the present invention prepares a polyionic liquid-MXene composite material based on the advantages of ionic liquids and two-dimensional materials. The composite material has a three-dimensional cross-linked hierarchical porous structure. The three-dimensional cross-linked hierarchical porous structure can provide an open and fast transmission channel. The porous structure is used to reduce the mass transfer resistance, which is beneficial to the penetration of the active ingredients of Cistanche deserticola. In addition, the polyionic liquid-MXene composite material is rich in hydroxyl groups, which is beneficial to the strengthening of the interlayer promotion transfer mechanism and the improvement of the selectivity of the active ingredients of Cistanche deserticola.

[0053] The polyionic liquid-MXene composite material of the present invention has good separation performance of the active ingredients of Cistanche deserticola, 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. A polyionic liquid-MXene composite material for separating and purifying active ingredients of Cistanche deserticola, characterized in that: The preparation method comprises the following steps: (1) Titanium aluminum carbide and hydrofluoric acid are added to a polytetrafluoroethylene container, mixed and stirred to obtain a solution A. After the reaction is completed, a viscous black substance B is formed. Then, the product B is washed to neutrality and dried to obtain a product P1. (2) 1-vinylimidazole, chloroform and 1,2-dibromoethane are uniformly dispersed to obtain a mixture C, and the mixture C is heated and stirred under reflux under nitrogen protection. After the reaction is completed, the obtained substance D is rotary evaporated to obtain a product P2. (3) P1, P2, ultrapure water, ethanol, butylene glycol and azobisisobutyronitrile are placed in a flask, dispersed evenly, heated and stirred to obtain substance E. Finally, the mixture E is washed and dried overnight to obtain the target composite material.

2. The method for preparing the polyionic liquid-MXene composite material according to claim 1, characterized in that: In step (1), the mass ratio of titanium aluminum carbide to hydrofluoric acid is 1:10-20. The reaction conditions are 20-50°C for 24-72 hours. The drying conditions are 50-100°C for 5-48 hours. In step (2), the amount of 1-vinylimidazole, chloroform and 1,2-dibromoethane is 1-10 mmol; 5-30 mmol; 1-5 mmol. The reaction conditions are 50-130° C. for 6-36 hours. In step (3), the amount ratio of P1, P2, ultrapure water, ethanol, butylene glycol and azobisisobutyronitrile is: 0.1-0.5g; 0.1-0.5g; 0.3-2.0g; 0.3-2.0g; 0.01-0.5g; 0.01-0.5g. The reaction conditions are 50-130°C for 6-36h. The drying conditions are 50-100°C for 6-48h.

3. Use of the composite material according to claim 1 in the separation and purification of active ingredients from Cistanche deserticola.

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