CN110746538B - Preparation method and application of loofah sponge-based imprinted membrane material with reinforced concrete-like structure - Google Patents

Preparation method and application of loofah sponge-based imprinted membrane material with reinforced concrete-like structure Download PDF

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CN110746538B
CN110746538B CN201910884716.5A CN201910884716A CN110746538B CN 110746538 B CN110746538 B CN 110746538B CN 201910884716 A CN201910884716 A CN 201910884716A CN 110746538 B CN110746538 B CN 110746538B
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membrane
artemisinin
loofah sponge
loofah
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白蒙起
兰义营
卢健
董泽清
吴易霖
孟敏佳
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Jiangsu University
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    • B01J20/26Synthetic macromolecular compounds
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    • C08J2497/02Lignocellulosic material, e.g. wood, straw or bagasse

Abstract

The invention belongs to the technical field of material preparation and separation, and discloses preparation and application of a loofah sponge base imprinted membrane material with a reinforced concrete-like structure, wherein the preparation method comprises the following steps: step 1, preparing loofah sponge; step 2, modifying the loofah sponge by dopamine; step 3, preparing an artemisinin molecularly imprinted polymer; and step 4, preparing the loofah vegetable sponge based artemisinin molecularly imprinted membrane. The molecularly imprinted membrane prepared by the loofah sponge impregnation and permeation method can effectively overcome the defects that the molecularly imprinted polymer cannot be fully contacted with a target molecule, the mechanical strength performance of the membrane is poor, elution of template molecules is time-consuming and even cannot be completely eluted, and the like, and has the advantages of simple synthesis, high selectivity efficiency and the like.

Description

Preparation method and application of loofah sponge-based imprinted membrane material with reinforced concrete-like structure
Technical Field
The invention belongs to the technical field of material preparation and separation, and particularly relates to a preparation method and application of a loofah sponge-based imprinted membrane material with a reinforced concrete-like structure.
Background
Artemisinin (Artemisinin) is a sesquiterpene lactone drug with peroxy groups extracted from stems and leaves of plant Artemisia annua by Chinese scientists, is an internationally recognized antimalarial specific drug with independent intellectual property rights, and is widely used in the world. Therefore, the artemisinin has wide development prospect and great development value. The extraction and separation of artemisinin mainly adopts methods of Soxhlet extraction, organic solvent extraction, water vapor extraction and the like, and the method of separation and extraction by adopting a molecular imprinting membrane is rarely reported.
The development and application of a Molecular Imprinted Membrane (MIM), which combines a Molecular Imprinted technology with a Membrane separation technology, is one of the most attractive studies. On one hand, the molecular imprinting technology generates a polymer through copolymerization of a functional monomer and a target molecule, then elutes the target molecule through a solvent, and finally a 'memory' cavity which can be completely matched with the original target molecule on a space shape and a determined functional group can be left in the polymer, and the cavity can be specifically combined with the target molecule in a mixture, so that the separation and analysis effects of a target object are achieved. On the other hand, the technology overcomes the defect that the current commercial membrane materials such as ultrafiltration, microfiltration and reverse osmosis membrane can not realize the selective separation of single substances, and provides a feasible and effective solution for separating specific molecules from the mixture with similar structure. However, the conventional molecularly imprinted membrane has many defects, such as insufficient contact between the molecularly imprinted polymer and the target molecule during the co-mixing membrane preparation process, poor mechanical strength of the membrane, time-consuming elution of the template molecule, and even incomplete elution, thereby limiting the imprinting effect.
Disclosure of Invention
Aiming at the problems in the prior art, the invention coats a layer of uniform membrane casting solution on the surface of the loofah sponge by a dipping and permeating method to construct a novel three-dimensional imprinted membrane similar to reinforced concrete. The membrane casting solution is uniformly coated and connected in a staggered manner on the basis of the loofah sponge, so that the imprinting recognition sites can be more fully contacted with a target object, and the mechanical strength performance of the imprinting membrane can be remarkably enhanced. Meanwhile, the template molecules can be quickly and completely eluted from the imprinted polymer by adopting an efficient and quick elution method, so that the effect of improving the molecular imprinting is achieved.
The invention prepares an effect imprinted membrane material capable of greatly improving molecular imprinting. The method has the advantages that the method provides a new idea for improving the imprinting effect of the traditional blend imprinting membrane from a novel angle, and solves the problems that the molecular imprinting polymer in the blend membrane cannot be fully contacted with a target molecule, the mechanical strength performance of the membrane is poor, the elution of template molecules is time-consuming and even cannot be completely eluted and the like to a certain extent.
A preparation method of loofah sponge base imprinted membrane material with reinforced concrete-like structure comprises the following steps:
step 1, preparing loofah sponge:
purchasing natural towel gourd, removing impurities and towel gourd seeds, transversely slicing, and washing with deionized water. Then soaking with sodium hydroxide solution, drying, repeating the operation to remove jelly and wax, and washing with deionized water to neutrality. And finally, transferring the mixture to a vacuum drying oven, and drying the mixture at a certain temperature to constant weight.
Step 2, modifying the loofah sponge with dopamine:
preparing a tris (hydroxymethyl) aminomethane buffer solution, adjusting the pH value of the solution, adding a certain amount of dopamine (PDA), completely soaking the loofah sponge in the obtained mixed solution, uniformly stirring, and then putting the loofah sponge into a shaking machine for reaction.
Step 3, preparing the artemisinin molecularly imprinted polymer:
weighing a certain amount of acetonitrile in a flask, adding artemisinin (Ars), acrylamide (MAA), Ethylene Glycol Dimethacrylate (EGDMA) and Azobisisobutyronitrile (AIBN), placing in a hot water bath, mechanically stirring for a period of time at a certain temperature, heating to a test temperature for continuous reaction, eluting the artemisinin by using a ferric chloride solution with a certain concentration after the reaction is finished until the artemisinin is not detected by ultraviolet, and then washing the product to be neutral for multiple times by using ethanol, thus finally obtaining the artemisinin Molecularly Imprinted Polymers (MIPs).
Step 4, preparing the loofah vegetable sponge based artemisinin molecularly imprinted membrane:
adding the MIPs obtained in the step (2) into dimethyl sulfoxide (DMSO), adding polyvinylidene fluoride (PVDF), and mechanically stirring uniformly at 40-50 ℃ to obtain a membrane casting solution; and (3) standing to remove air bubbles in the membrane casting solution, pouring the membrane casting solution into a beaker, adding the loofah sponge obtained in the step one, and standing for a period of time to fill the membrane casting solution. Then taking out the loofah sponge and removing the redundant membrane casting solution. And finally, slowly immersing the membrane into deionized water to complete phase transformation, thereby obtaining the loofah vegetable sponge artemisinin Molecularly Imprinted Membrane (MIM).
In the step 1, the sodium hydroxide with the mass fraction of 10 percent is used, and the sodium hydroxide is taken out and dried after being soaked for 10min, the operation time is 3.0h after repeated operation, and the temperature of a vacuum drying oven is 60 ℃.
In the step 2, the concentration of the tris (hydroxymethyl) aminomethane buffer solution is 0.01mol/L, the pH value of the solution is 8.5, and the dosage ratio of the tris (hydroxymethyl) aminomethane buffer solution to PDA is 100 mL: 0.1-0.2 g; the reaction time is 8-12 h.
In the step 3, the molar weight ratio of the template molecule artemisinin, the functional monomer acrylamide, the cross-linking agent EGDMA and the initiator AIBN is 1:4: 20: 0.9, the test temperature of the reaction is 60 ℃, the time is 10 hours, and the concentration of the iron chloride solution of the eluent is 0.1 mmol/L.
In the step 4, when the loofah sponge based artemisinin molecularly imprinted membrane is prepared, the mass of the PVDF powder accounts for 2% -10% of the membrane casting solution, the mass of the MIPs accounts for 0.5% -2.0% of the membrane casting solution, and the rest is the amount of the solvent DMSO. The mechanical stirring time is 5 hours; soaking in deionized water for at least 30 min.
For comparison, non-artemisinin molecularly imprinted polymers (NIPs) were prepared in the same manner as in steps (1) - (3) of the method described above, except that the template molecule, artemisinin, was not added. For comparison, loofah sponge based non-artemisinin molecularly imprinted membrane (NIM) preparation is the same as above method steps (1) - (4) except that no template molecule artemisinin is added.
The loofah sponge in the technical scheme has the functions of providing a reinforced concrete framework, supporting the membrane casting solution and greatly enhancing the mechanical strength performance of the membrane.
The dopamine in the technical scheme has the function of modifying the loofah sponge, increasing the adhesion function of the loofah sponge, and enabling the casting solution to be coated on the loofah sponge more firmly.
The artemisinin described in the above technical scheme acts as a template molecule.
The acrylamide in the technical scheme is used as a functional monomer.
The ethylene glycol dimethacrylate in the technical scheme is used as a cross-linking agent.
The azobisisobutyronitrile in the technical scheme has the function of an initiator.
The ferric chloride solution in the technical scheme has the function of an eluent, and can quickly and efficiently elute the template molecule artemisinin.
The dimethyl sulfoxide in the technical scheme is used as a solvent to dissolve PVDF so as to prepare a membrane casting solution.
The PVDF described in the above technical scheme acts as a matrix.
The deionized water described in the above step 4 functions as a phase inversion agent.
The loofah sponge-based imprinted membrane material with the similar reinforced concrete structure prepared by the invention is used for selectively identifying and separating artemisinin molecules in a mixture.
The invention has the technical advantages that:
(1) the coating condition of the casting solution in the loofah sponge is regulated and controlled by changing the proportion of solid matters in the casting solution, and the degree of staggered connection of the casting solution, so that a novel three-dimensional imprinted membrane structure similar to reinforced concrete is constructed, the purpose of fully contacting an imprinting identification site with a target object is achieved, meanwhile, the mechanical strength performance of the imprinted membrane can be obviously enhanced, and the molecular imprinting efficiency is improved.
(2) By adopting an efficient and rapid elution method, the template molecules can be rapidly and completely eluted from the imprinted polymer, thereby achieving the effect of improving the molecular imprinting.
(3) The loofah vegetable sponge based artemisinin molecularly imprinted membrane obtained by the method has the advantages of stable mechanical strength, good thermal stability, rapid adsorption kinetics property and obvious artemisinin molecule recognition performance.
Drawings
FIG. 1 is a transmission diagram of an artemisinin molecularly imprinted polymer;
FIG. 2 is a diagram of a loofah vegetable sponge based artemisinin molecularly imprinted membrane;
FIG. 3 is the adsorption isotherm curves of MIM and NIM for artemisinin at 298K;
FIG. 4 is a tensile force curve diagram of a loofah vegetable sponge artemisinin molecularly imprinted membrane (LM for short) and a blank PVDF membrane (PM for short).
Detailed description of the preferred embodiments
The invention is further illustrated by the following examples.
Example one
(1) Preparing loofah sponge:
taking natural fructus Luffae, removing impurities and semen Luffae, transversely slicing, and washing with deionized water for 30 min. Soaking in sodium hydroxide solution for 10min, oven drying, repeating the operation for 3.0 hr, removing jelly and wax, and washing with deionized water for 30 min. Finally, the mixture is transferred to a vacuum drying oven and dried for 24 hours at 60 ℃.
(2) The dopamine modified loofah sponge comprises:
preparing a tris (hydroxymethyl) aminomethane buffer solution with the concentration of 0.01mol/L, adjusting the pH of the solution to 8.5, and adding 0.1g of dopamine (PDA) and loofah sponge. After being stirred uniformly, the mixture is put into a shaking machine to react for 8 hours.
(3) Preparation of artemisinin molecularly imprinted polymer
60mL of acetonitrile was weighed into a flask, and 28.2mg of artemisinin, 28.4mg of acrylamide (MAA), 396.4mg of Ethylene Glycol Dimethacrylate (EGDMA) and 10mg of Azobisisobutyronitrile (AIBN) were added to the flask, and the mixture was mechanically stirred at 50 ℃ for a while, and then heated to 60 ℃ to continue the reaction for 10 hours. After the reaction is finished, eluting the artemisinin by using ferric chloride solution (0.1mmol/L) until the artemisinin can not be detected by ultraviolet, and then washing the product for multiple times by using ethanol to finally obtain the artemisinin imprinted molecular polymer (MIPs).
(4) Preparing the loofah sponge based artemisinin molecularly imprinted membrane:
adding 0.1g of MIPs obtained in the step (3) into 19.5g of dimethyl sulfoxide (DMSO), adding 0.4g of polyvinylidene fluoride (PVDF), and mechanically stirring uniformly at 50 ℃ to obtain a membrane casting solution; and (3) standing to remove air bubbles in the membrane casting solution, pouring the membrane casting solution into a beaker, adding the loofah sponge obtained in the step one, and standing for 5min to fill the membrane casting solution. Then taking out the loofah sponge and removing the redundant membrane casting solution. And finally, slowly immersing the membrane into deionized water to complete phase transformation, thereby obtaining the loofah vegetable sponge artemisinin molecularly imprinted membrane.
For comparison, the preparation method of the non-imprinted membrane was the same as the above except that the template molecule artemisinin was not added.
Example two
(1) Preparing loofah sponge:
taking natural fructus Luffae, removing impurities and semen Luffae, transversely slicing, and washing with deionized water for 30 min. Soaking in sodium hydroxide solution for 10min, oven drying, repeating the operation for 3.0 hr, removing jelly and wax, and washing with deionized water for 30 min. Finally, the mixture is transferred to a vacuum drying oven and dried for 24 hours at 60 ℃.
(2) The dopamine modified loofah sponge comprises:
preparing a tris (hydroxymethyl) aminomethane buffer solution with the concentration of 0.01mol/L, adjusting the pH of the solution to 8.5, and adding 0.15g of dopamine (PDA) and loofah sponge. After being stirred uniformly, the mixture is put into a shaking machine to react for 10 hours.
(3) Preparation of artemisinin molecularly imprinted polymer
60mL of acetonitrile was weighed into a flask, and 35.25mg of artemisinin, 35.5mg of acrylamide (MAA), 495.5mg of Ethylene Glycol Dimethacrylate (EGDMA) and 12.5mg of Azobisisobutyronitrile (AIBN) were added and placed in a hot water bath, and after mechanical stirring was carried out at 50 ℃ for a while, the temperature was raised to 60 ℃ to continue the reaction for 10 hours. After the reaction is finished, eluting artemisinin by using ferric chloride solution (0.1mmol/L) until artemisinin can not be detected by ultraviolet, and then washing the product for multiple times by using ethanol to finally obtain the artemisinin imprinted polymer (MIPs).
(4) Preparing the loofah sponge based artemisinin molecularly imprinted membrane:
adding 0.25g of MIPs obtained in the step (3) into 18.75g of dimethyl sulfoxide (DMSO), adding 1.0g of polyvinylidene fluoride (PVDF), and mechanically stirring uniformly at 50 ℃ to obtain a membrane casting solution; and (3) standing to remove air bubbles in the membrane casting solution, pouring the membrane casting solution into a beaker, adding the loofah sponge obtained in the step one, and standing for 5min to fill the membrane casting solution. Then taking out the loofah sponge and removing the redundant membrane casting solution. And finally, slowly immersing the membrane into deionized water to complete phase transformation, thereby obtaining the loofah vegetable sponge artemisinin molecularly imprinted membrane.
For comparison, the preparation method of the non-imprinted membrane was the same as the above except that the template molecule artemisinin was not added.
EXAMPLE III
(1) Preparing loofah sponge:
taking natural fructus Luffae, removing impurities and semen Luffae, transversely slicing, and washing with deionized water for 30 min. Soaking in sodium hydroxide solution for 10min, oven drying, repeating the operation for 3.0 hr, removing jelly and wax, and washing with deionized water for 30 min. Finally, the mixture is transferred to a vacuum drying oven and dried for 24 hours at 60 ℃.
(2) The dopamine modified loofah sponge comprises:
preparing a tris (hydroxymethyl) aminomethane buffer solution with the concentration of 0.01mol/L, adjusting the pH of the solution to 8.5, and adding 0.2g of dopamine (PDA) and loofah sponge. After being stirred uniformly, the mixture is put into a shaking machine to react for 12 hours.
(3) Preparation of artemisinin molecularly imprinted polymer
60mL of acetonitrile is measured in a flask, 42.3mg of artemisinin, 42.6mg of acrylamide (MAA), 594.6mg of Ethylene Glycol Dimethacrylate (EGDMA) and 15mg of Azobisisobutyronitrile (AIBN) are added into the flask, the mixture is mechanically stirred at 50 ℃ for a period of time, and then the temperature is raised to 60 ℃ for continuous reaction for 10 hours. After the reaction is finished, eluting artemisinin by using ferric chloride solution (0.1mmol/L) until artemisinin can not be detected by ultraviolet, and then washing the product for multiple times by using ethanol to finally obtain the artemisinin imprinted polymer (MIPs).
(4) Preparing the loofah sponge based artemisinin molecularly imprinted membrane:
adding 0.4g of MIPs obtained in the step (3) into 17.6g of dimethyl sulfoxide (DMSO), adding 2.0g of polyvinylidene fluoride (PVDF), and mechanically stirring uniformly at 50 ℃ to obtain a membrane casting solution; and (3) standing to remove air bubbles in the membrane casting solution, pouring the membrane casting solution into a beaker, adding the loofah sponge obtained in the step one, and standing for 5min to fill the membrane casting solution. Then taking out the loofah sponge and removing the redundant membrane casting solution. And finally, slowly immersing the membrane into deionized water to complete phase transformation, thereby obtaining the loofah vegetable sponge artemisinin molecularly imprinted membrane.
For comparison, the preparation method of the non-imprinted membrane was the same as the above except that the template molecule artemisinin was not added.
FIG. 2 is a diagram of a loofah vegetable sponge based artemisinin molecularly imprinted membrane; from fig. 2, it can be seen that the invention prepares a novel three-dimensional imprinted membrane structure of reinforced concrete.
(1) Static adsorption experiment
Adding certain mass of retinervus Luffae fructus-based imprinted membrane into corresponding test solution, oscillating in constant temperature water bath, examining influence of initial concentration of different adsorption solutions on imprinted membrane, measuring unadsorbed artemisinin molecule concentration by HPLC after adsorption, and calculating adsorption capacity (Q) according to the resulte,mg/g):
Figure BDA0002206950000000061
Wherein C is0(mg/L) and Ce(mg/L) is the initial concentration of artemisinin and the equilibrium adsorption concentration, respectively. V (mL) and W (mg) are the volume of the solution and the mass of the different membranes, respectively.
FIG. 3 is the adsorption isotherm curves of MIM and NIM for artemisinin at 298K. As shown in fig. 3, the amount of adsorption of the MIM and NIM to Ars increased rapidly within the first 20min and reached equilibrium after about 30min, while the nonspecific adsorption of non-imprinted membranes to Ars was also saturated after 50 min. The MIM surface has a faster Ars adsorption rate due to more binding sites matching the Ars molecules than NIM. Compared with the blank NIM, the adsorption Ars of the MIM has excellent dynamic performance, because the recognition sites are positioned on the surface of the PVDF membrane of the basal membrane with accessibility in the process of synthesizing the membrane by magnetic force induction, the mass transfer rate is faster, and the adsorption balance can be reached faster.
(2) Selectivity test
Fixing the retinervus Luffae fructus basal membrane on a constant-pressure flat membrane machine, adding ethanol solution containing artemisinin, artesunate and artemether as substrate into the storage tank, starting the machine, sampling at certain time interval, measuring the substrate concentration of penetrating fluid, and calculating the adsorption amount.
TABLE 1 Selective adsorption parameters of MIM and NIM for different substrates
Figure BDA0002206950000000062
(3) Tensile test
Several 10mm long sample strips are cut and clamped at the upper end and the lower end of a tension fracture machine (composed of a constant speed motor, a clamp and a spring scale), a series of testing parameters are set, and the tensile capacity of the film is tested. The elongation of the film under a certain pressure is calculated. EB (%) ═ distance L from punctuation at break1Distance L from origin0) Distance L between original points0×100%
Fig. 4 is a tensile curve of the loofah sponge film (LM) and the blank PVDF film (PM). As shown in the figure, the elongation rates of the LM and the PM are increased along with the increase of the tensile force, the PM is completely broken when the elongation rate reaches 0.19, and the LM has strong tensile strength and is not completely broken until reaching 1.21, because the reinforced concrete-like loofah sponge film has good mechanical properties, and a strong tensile effect can be achieved.

Claims (6)

1. A preparation method of loofah sponge base imprinted membrane material with reinforced concrete-like structure is characterized by comprising the following steps:
step 1, preparing loofah sponge:
purchasing natural luffa, removing impurities and luffa seeds, transversely slicing, washing with deionized water, soaking with sodium hydroxide solution, oven drying, repeating the operation to remove jelly and wax, washing with deionized water to neutrality, transferring to a vacuum drying oven, and drying at a certain temperature to constant weight;
step 2, modifying the loofah sponge with dopamine:
preparing a tris (hydroxymethyl) aminomethane buffer solution, adjusting the pH value of the solution, adding a certain amount of dopamine PDA, and completely soaking the loofah sponge in the obtained mixed solution; after being uniformly stirred, the mixture is put into a shaking machine for reaction;
step 3, preparing the artemisinin molecularly imprinted polymer:
weighing a certain amount of acetonitrile in a flask, adding artemisinin Ars, acrylamide AM, ethylene glycol dimethacrylate EGDMA and azobisisobutyronitrile AIBN, placing in a hot water bath, mechanically stirring for a period of time at a certain temperature, heating to a test temperature for continuous reaction, eluting the artemisinin by using a ferric chloride solution with a certain concentration after the reaction is finished until the artemisinin cannot be detected by ultraviolet, immediately washing the product to be neutral by using ethanol for multiple times, and finally obtaining the artemisinin imprinted polymer MIPs;
step 4, preparing the loofah vegetable sponge based artemisinin molecularly imprinted membrane:
adding the MIPs obtained in the step (3) into dimethyl sulfoxide DMSO, adding polyvinylidene fluoride (PVDF), and mechanically stirring uniformly at a certain temperature to obtain a membrane casting solution; standing to remove air bubbles in the membrane casting solution, pouring the membrane casting solution into a beaker, adding the loofah sponge obtained in the step (1), standing for a period of time to fill the membrane casting solution, taking out the loofah sponge, and removing the redundant membrane casting solution; and finally, slowly immersing the membrane into deionized water to complete phase transformation, thereby obtaining the loofah vegetable sponge artemisinin molecularly imprinted membrane.
2. The preparation method of the loofah sponge-based imprinted membrane material with the reinforced concrete-like structure as claimed in claim 1, wherein in step 1, the sodium hydroxide is used in a mass fraction of 10%, and the operation time is 3.0h after soaking for 10min, taking out and drying, and the temperature of the vacuum drying oven is 60 ℃.
3. The preparation method of loofah sponge-based imprinted membrane material like reinforced concrete according to claim 1, wherein in step 2, the concentration of tris (hydroxymethyl) aminomethane buffer solution is 0.01mol/L, the pH value of the solution is 8.5, and the ratio of the amount of tris (hydroxymethyl) aminomethane buffer solution to the amount of PDA is 100 mL: 0.1-0.2 g; the reaction time is 8-12 h.
4. The preparation method of the loofah sponge-based imprinted membrane material with the reinforced concrete-like structure according to claim 1, wherein in step 3, the molar weight ratio of the template molecule artemisinin, the functional monomer acrylamide, the cross-linking agent EGDMA and the initiator AIBN is 1:4: 20: 0.9, the test temperature of the reaction is 60 ℃, the time is 10 hours, and the concentration of the iron chloride solution of the eluent is 0.1 mmol/L.
5. The preparation method of loofah sponge-based imprinted membrane material with a similar 'reinforced concrete' structure as in claim 1, wherein in step 4, during the preparation of loofah sponge-based artemisinin molecularly imprinted membrane, the mass of PVDF powder accounts for 2% -10% of the membrane casting solution, the mass of MIPs accounts for 0.5% -2.0% of the membrane casting solution, and the rest is the amount of solvent DMSO; the mechanical stirring time is 5 hours; the temperature is 40-50 ℃; soaking in deionized water for at least 30 min.
6. Use of the loofah sponge-based imprinted membrane material with a similar reinforced concrete structure prepared by the preparation method of any one of claims 1-5 in selective recognition and separation of artemisinin molecules in a mixture.
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