CN116675897A - Organic polymer aerogel for separating active components of traditional Chinese medicine and preparation method thereof - Google Patents
Organic polymer aerogel for separating active components of traditional Chinese medicine and preparation method thereof Download PDFInfo
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- CN116675897A CN116675897A CN202310625178.4A CN202310625178A CN116675897A CN 116675897 A CN116675897 A CN 116675897A CN 202310625178 A CN202310625178 A CN 202310625178A CN 116675897 A CN116675897 A CN 116675897A
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- China
- Prior art keywords
- traditional chinese
- organic polymer
- chinese medicine
- polymer aerogel
- aerogel
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
- A61K36/18—Magnoliophyta (angiosperms)
- A61K36/185—Magnoliopsida (dicotyledons)
- A61K36/71—Ranunculaceae (Buttercup family), e.g. larkspur, hepatica, hydrastis, columbine or goldenseal
- A61K36/718—Coptis (goldthread)
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
- A61K36/18—Magnoliophyta (angiosperms)
- A61K36/185—Magnoliopsida (dicotyledons)
- A61K36/35—Caprifoliaceae (Honeysuckle family)
- A61K36/355—Lonicera (honeysuckle)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
- C08G12/32—Melamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
- C08G8/22—Resorcinol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2236/00—Isolation or extraction methods of medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicine
- A61K2236/30—Extraction of the material
- A61K2236/33—Extraction of the material involving extraction with hydrophilic solvents, e.g. lower alcohols, esters or ketones
- A61K2236/333—Extraction of the material involving extraction with hydrophilic solvents, e.g. lower alcohols, esters or ketones using mixed solvents, e.g. 70% EtOH
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2236/00—Isolation or extraction methods of medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicine
- A61K2236/50—Methods involving additional extraction steps
- A61K2236/51—Concentration or drying of the extract, e.g. Lyophilisation, freeze-drying or spray-drying
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2236/00—Isolation or extraction methods of medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicine
- A61K2236/50—Methods involving additional extraction steps
- A61K2236/53—Liquid-solid separation, e.g. centrifugation, sedimentation or crystallization
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
- C08J2205/026—Aerogel, i.e. a supercritically dried gel
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2361/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08J2361/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention relates to the technical field of traditional Chinese medicine separation, and discloses an organic polymer aerogel for separating traditional Chinese medicine active components and a preparation method thereof. The organic polymer aerogel prepared by the method is green and nontoxic, has a green, mild and efficient adsorption process, can be recycled, and can be widely used for the selective separation of active components of traditional Chinese medicines.
Description
Technical Field
The invention relates to the technical field of traditional Chinese medicine separation, in particular to an organic polymer aerogel for separating active components of traditional Chinese medicines and a preparation method thereof.
Background
The Chinese medicine is a natural medicine for preventing and treating diseases and having the functions of rehabilitation and health care and a processing substitute thereof by taking the theory of the Chinese medicine as a guide. However, the source of pharmacological activity of the traditional Chinese medicine is only one or one kind of chemical components (such as effective component alkaloid of rhizoma coptidis, effective component chlorogenic acid of honeysuckle and effective component flavonoids of ginkgo leaf). Because traditional Chinese medicine is a multicomponent system and lacks effective separation technology, the research of pharmacological mechanism of active ingredients in traditional Chinese medicine and industrialized application still face great difficulties and challenges. Therefore, the selective separation of the active ingredients of the traditional Chinese medicine is an important precondition for ensuring the reliability and safety of pharmacological research and clinical application.
The traditional Chinese medicine separation and purification strategies currently prevailing include precipitation methods (such as salting out separation), chromatography methods (such as high-speed countercurrent chromatography and high-performance liquid chromatography), adsorption methods (such as column chromatography and membrane filtration) and the like. However, precipitation and chromatographic separation techniques are very likely to cause the harm of activity loss or secondary pollution of active ingredients in traditional Chinese medicines due to the introduction of strong acid, strong alkali or organic reagent; adsorption separation is considered as the most promising method for separating traditional Chinese medicines due to the advantages of green temperature and recycling. To date, a great deal of literature reports that separation of active ingredients of various traditional Chinese medicines can be achieved by using macroporous resin, ion exchanger, molecularly imprinted polymer, mesoporous silica nanoparticles, surface functionalized magnetic nanoparticles, carbon nanotubes and graphene oxide carbon-based materials. Besides, xia Xianming (CN 100400145C) discloses a traditional Chinese medicine purification microfiltration membrane, which adopts a microfiltration membrane synthesized by low-cost raw materials to realize the high-value application of separating the effective components of the traditional Chinese medicine; shao Lu (CN 105413498B) discloses a method for modifying microfiltration and ultrafiltration membranes for separating traditional Chinese medicines, which solves the problems of poor hydrophilicity and poor pollution resistance of the conventional commercial microfiltration and ultrafiltration membranes; chongqing academy of technology Liao Xiaoling (CN 101658764B) discloses a preparation method of a double-layer ceramic filter membrane for separating and refining traditional Chinese medicines, and the separation and refining of the traditional Chinese medicines are realized by controlling the porosity and pore size of porous ceramics; li Qifa (CN 102399259B) discloses a method for extracting liriope spicata saponin B from the underground part of Hubei mountain dwarf lilyturf tuber by adopting macroporous resin combined with silica gel column chromatography, which overcomes the defect of repeated purification by sephadex and C18 reverse chromatography column; wen Huansong (CN 102993143B) discloses a method for rapidly separating lithospermic acid monomers from Salvia Miltiorrhiza by macroporous resin enrichment and high performance preparative liquid chromatography. The great advantage of adsorption separation causes the research of adsorption separation materials for active ingredients of traditional Chinese medicines. However, membrane filtration is generally a selective separation based on size sieving effect, which has insufficient separation selectivity and is affected by limited adsorption sites and specific surface area; the macroporous resin has higher specific surface area and rich functional groups, but the irregulability leads to the efficacy and hypodynamia in the application of separating traditional Chinese medicines. In summary, in the research of adsorption separation of active ingredients of traditional Chinese medicine, the poor adsorption selectivity and insufficient adsorption efficiency are all the important scientific problems to be solved urgently.
The aerogel is a three-dimensional porous material with gas medium formed by interconnecting colloid particles or polymers under certain conditions, and the special structure endows the aerogel with excellent performance, such as extremely low volume density (about 0.003-0.005 g/cm 3 ) High porosity (98% -99%), large specific surface area (1500 m) 2 /g) and abundant surface functional groups, etc. The organic polymer aerogel is obtained by combining polycondensation reaction and supercritical drying process and has high pore volume (0.25-1.25 cm) 3 Per g), extremely high specific surface area (400-1000 m) 2 And/g) and rich functional groups. In subsequent continuous research, it was found that the morphology of the organic polymer aerogel can be varied as a function of different synthesis parameters. This feature allows tailoring the internal structure and chemical function of these porous materials on the nanometer scale, making them particularly suitable for diverse applications in the crossover field. Nevertheless, the potential of organic polymer aerogels is still not fully exploited, and to our knowledge, no related research and report on the application of aerogels in the separation of active ingredients of traditional Chinese medicines is currently available. The chemical structure of the effective components of the traditional Chinese medicine has different physical and chemical properties, such as polarity difference, molecular size difference and the like, and in order to realize the selective separation of the effective components of the traditional Chinese medicine, the matched aerogel materials are required to be selected according to the physical and chemical properties of the effective components of the traditional Chinese medicine, and the physical structure and chemical functional characteristics of the aerogel materials are finely regulated so as to adapt to the selective separation of the effective components of the traditional Chinese medicine in different systems.
Disclosure of Invention
The invention aims to: aiming at the problems in the prior art, the invention provides the organic polymer aerogel for separating the active components of the traditional Chinese medicine and the preparation method thereof, and the pore size and the surface potential of the organic polymer aerogel are accurately regulated and controlled, so that the active components of the traditional Chinese medicine are efficiently and selectively adsorbed and separated. The organic polymer aerogel prepared by the method is green and nontoxic, has a green, mild and efficient adsorption process, can be recycled, and can be widely used for the selective separation of active components of traditional Chinese medicines.
The technical scheme is as follows: the invention provides an organic polymer aerogel for separating active components of traditional Chinese medicines and a preparation method thereof, comprising the following steps:
step one, preparing organic polymer aerogel:
adding ammonia organic compound and aldehyde organic compound reaction monomer into a certain amount of deionized water, dissolving completely, homogenizing, adding catalyst, and stirring to obtain prepolymerized solution; hydrochloric acid or sodium hydroxide is used for regulating the pH value of the pre-polymerized solution, then the pre-polymerized solution is put into a reaction kettle for sealing, and a sol-gel process of polycondensation reaction is carried out under the conditions of high temperature and high pressure to obtain the organic polymer hydrogel; fully replacing the organic polymer hydrogel with ethanol, and drying to obtain organic polymer aerogel;
or adding a phenolic organic compound and an aldehyde organic compound reaction monomer into a certain amount of deionized water, dissolving completely and homogenizing, adding a catalyst, stirring to obtain a prepolymerization solution, placing the prepolymerization solution into a reaction kettle for sealing, and performing a sol-gel process of polycondensation reaction under high temperature and high pressure to obtain the organic polymer hydrogel; fully replacing the organic polymer hydrogel with ethanol, and drying to obtain organic polymer aerogel;
step two, selectively separating active components of the traditional Chinese medicine:
s1, pulverizing fresh traditional Chinese medicines, dispersing into an alcohol/water mixed solution, stirring, carrying out ultrasonic treatment, centrifuging, and collecting supernatant to obtain a crude traditional Chinese medicine extract;
s2, placing the organic polymer aerogel serving as an adsorbent into a crude traditional Chinese medicine extracting solution for adsorption, oscillating at constant temperature, and centrifuging to obtain aerogel enriched with active components;
s3, placing the aerogel enriched with the active components in an eluent, and stirring at room temperature until desorption is complete to obtain a renewable aerogel adsorbent and a traditional Chinese medicine active component eluent; the eluent of the active components of the traditional Chinese medicine is concentrated by rotary evaporation to obtain a high-purity dry extract of the active components of the traditional Chinese medicine.
Further, in the first step, the molar ratio of the ammonia organic compound to the aldehyde organic compound is 1:2-6;
and/or, in the first step, the overall concentration of the ammonia organic compound is 0.5-2 mol/L;
and/or in the first step, the molar ratio of the ammonia organic compound to the catalyst is 10-100:1;
and/or, in the first step, hydrochloric acid or sodium hydroxide adjusts the pH value of the pre-polymerization solution to 1.5-3.0;
and/or, in the first step, when the ammonia organic compound and the aldehyde organic compound react, the specific conditions of the reaction are as follows: the reaction temperature is 60-120 ℃, and the reaction time is 8-12 h.
Further, in the first step, the molar ratio of the phenolic organic compound to the aldehyde organic compound is 1:3-5;
and/or, in the first step, the total concentration of the phenolic organic compound is 0.5-2 mol/L;
and/or in the first step, the molar ratio of the phenolic organic compound to the catalyst is 5-500:1;
and/or, in the first step, when the phenolic organic compound is reacted with the aldehyde organic compound, the specific conditions of the reaction are as follows: the reaction temperature is 100-180 ℃ and the reaction time is 10-14 h.
Further, in the first step, the specific conditions of the drying are as follows: CO at 60-80 ℃ and 10-15 MPa 2 And (5) supercritical drying.
In step S1, the Chinese medicine is a Chinese herbal medicine source with alkaloid as an active ingredient or a Chinese herbal medicine source with chlorogenic acid as an active ingredient.
Further, the Chinese herbal medicine source with alkaloid as the effective component is coptis chinensis, epimedium herb and poppy;
and/or the Chinese herbal medicine sources with chlorogenic acid as the active ingredients are honeysuckle, jerusalem artichoke and eucommia ulmoides leaves.
Further, in the step two S1, the alcohol/water mixed solution is an ethanol aqueous solution with a volume fraction of 10% -90%.
Further, in the second step S2, specific conditions of the adsorption are as follows:
the solid-liquid ratio of the adsorbent to the crude extract of the traditional Chinese medicine is 1 g:100-500 mL, the adsorption pH is 3.0-11.0, the adsorption temperature is 20-80 ℃, and the adsorption time is 1-6 h.
In step S3, the eluent is one or more of ethanol, methanol, hydrochloric acid and deionized water;
and/or in the second step S3, the volume of the eluent is 0.5-5 times of the volume of the crude extract of the traditional Chinese medicine in the second step S2.
Preferably, in the step two S1, the specific condition of the centrifugation is 10000-11000 rpm for 10-15 min;
and/or in the second step S1, the specific condition of stirring is that stirring is carried out at 50-70 ℃ for 1-2 h.
The beneficial effects are that: compared with the prior art, the invention has the following specific beneficial effects:
(1) Besides the small molecules as active components, the chemical components of the Chinese herbal medicine further comprise biological macromolecule non-active components such as starch, protein, cellulose and the like without any pharmacological activity. The organic polymer aerogel has the advantages of high specific surface area and abundant surface functional groups, and can be used for efficiently and selectively adsorbing and separating active components of traditional Chinese medicines based on the synergistic effect of size screening and polarity matching. The invention combines the sol-gel process of polycondensation reaction with CO 2 The supercritical drying process controls nucleation, growth and linking states of polymer nano particles through monomer and process parameter optimization, so as to accurately regulate and control the aperture size of the organic polymer aerogel, and ensures that small-molecule active ingredients are free in the deep structure of the aerogel and simultaneously prevent non-bioactive macromolecules from entering by utilizing the size screening principle similar to a gate effect, thereby providing guarantee for separation selectivity of active components of the traditional Chinese medicine.
(2) Whether the alkaloid contains an alkaloid alkaline organic compound containing negative oxidation state nitrogen or chlorogenic acid organic acid compound rich in carboxylic acid in chlorogenic acid, the rich characteristic functional groups determine that the molecular polarity of the compound is stronger. According to the principle of similar compatibility, a large number of adsorption sites on the surface of the organic polymer aerogel endow the organic polymer aerogel with strong specific affinity with the effective components of the traditional Chinese medicine, and a foundation is laid for efficiently and selectively separating the effective components of the traditional Chinese medicine.
(3) The pore size and surface electrical property of the organic polymer aerogel are finely customized in a process parameter optimization mode to form a good structure-activity relationship between the aerogel and the traditional Chinese medicine active components, so that a novel selective separation method of the traditional Chinese medicine active components based on the synergistic effect of size screening and specific affinity is formed. The method has the advantages of simple and flexible process, low cost and high separation efficiency. The adsorption amount of the alkaloid on the phenolic polymer aerogel is up to 593 mg/g, and the purity is improved from 39.2% to 90.2%; the adsorption capacity of chlorogenic acid on melamine polymer aerogel reaches 151 mg/g, and the purity is improved from 10.5% to 60.5%.
(4) The organic polymer aerogel prepared by the method is green, nontoxic and recyclable, and the adsorption process is green, mild and efficient, and can be widely used for the selective separation of active components of traditional Chinese medicines.
Drawings
FIG. 1 is a process flow diagram of the selective adsorption separation of active components of traditional Chinese medicine by using an organic polymer aerogel according to the invention;
fig. 2 is a scanning electron microscope image (left) and a pore size distribution graph (right) of the phenolic polymer aerogel prepared in embodiment 1;
FIG. 3 shows the molecular weight (left) and the distribution difference (right) of protein and polysaccharide in the crude extract of Coptidis rhizoma before and after the crude extract of Coptidis rhizoma is separated by phenolic polymer aerogel in embodiment 2;
FIG. 4 is a scanning electron microscope image of the melamine polymer aerogel prepared in embodiment 4;
fig. 5 is a liquid chromatogram of chlorogenic acid in the crude extract of honeysuckle flower before and after separation by the melamine polymer aerogel in embodiment 5.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
Embodiment 1:
(1) Preparation of phenolic Polymer aerogel
Weighing resorcinol, adding the resorcinol into deionized water (the mol ratio of the resorcinol to the deionized water is 3:500), and stirring and dissolving at room temperature; to resorcinol solutionAdding formaldehyde solution (37%) and sodium hydroxide catalyst (the mol ratio of resorcinol to sodium hydroxide is 100:1) for 15 min to obtain a prepolymerized solution; placing the prepolymerization solution into a reaction kettle, and curing 12 h at 100 ℃ to obtain phenolic polymer hydrogel; CO after the hydrogel is fully replaced by ethanol 2 Supercritical drying to obtain phenolic polymer aerogel;
(2) Selectively separating alkaloid from the effective components of rhizoma Coptidis:
a) Taking fresh traditional Chinese medicine Huang Lian powder, and dispersing the powder in 50% (v/v) alcohol/water mixed solution according to a solid-to-liquid ratio of 1:30 (g/mL); 50. stirring at a temperature of 1 h, soaking, ultrasonic extracting at 24kHz,240W for 1 h, centrifuging at 10000 rpm for 15 min, and collecting filtrate to obtain Coptidis rhizoma crude extract;
b) Transferring Coptidis rhizoma crude extract into conical flask, and adding phenolic polymer aerogel adsorbent according to solid-liquid ratio of 3:800 (g/mL); placing the conical flask into a constant temperature water bath oscillator, and oscillating at constant temperature (120 rpm) until adsorption separation is balanced; centrifuging (10000 rpm,15 min) and separating, and collecting the phenolic polymer aerogel adsorbent enriched with alkaloids;
c) Adding the phenolic polymer aerogel enriched with the alkaloids into 50 mL methanol eluent containing 1% hydrochloric acid, and stirring at room temperature until complete desorption to obtain a renewable phenolic polymer aerogel adsorbent and an alkaloid eluent; the alkaloid eluent is concentrated by rotary evaporation to obtain high-purity alkaloid extract dry product. The pore size distribution of the phenolic polymer aerogel is 10-20 nm, and the surface potential is-38.35 mV; the adsorption capacity of the alkaloid is 593 mg/g, and the purity of the alkaloid is improved to 68.4%.
Fig. 2 is a scanning electron microscope image (left) and a pore size distribution curve (right) of the phenolic polymer aerogel in embodiment 1. As can be seen from the figure, the average pore size of the phenolic polymer aerogel prepared by the process is in the range of 10-20 nm.
Embodiment 2:
(1) Preparation of phenolic Polymer aerogel
Resorcinol was weighed into deionized water (molar ratio of resorcinol to deionized water: 3:200) and the chamberStirring and dissolving at the temperature; sequentially adding formaldehyde solution (37%) and sodium hydroxide catalyst (the mol ratio of resorcinol to sodium hydroxide is 10:1) into resorcinol solution, and stirring for 15 min to obtain a prepolymerized solution; placing the prepolymerization solution into a reaction kettle, and curing the prepolymerization solution at 100 ℃ for 12 h to obtain phenolic polymer hydrogel; CO after the hydrogel is fully replaced by ethanol 2 Supercritical drying to obtain phenolic polymer aerogel;
(2) Selectively separating alkaloid from the effective components of rhizoma Coptidis:
a) Taking fresh traditional Chinese medicine Huang Lian powder, and dispersing the powder in a 20% (v/v) alcohol/water mixed solution according to a solid-to-liquid ratio of 1:30 (g/mL); 50. stirring at a temperature of 1 and h, soaking thoroughly, and then extracting with ultrasound (24 kHz, 240W) for 1 h; centrifuging (10000 rpm,15 min) the suspension after extraction, filtering, and collecting filtrate to obtain Coptidis rhizoma crude extract;
b) Transferring Coptidis rhizoma crude extract into conical flask, and adding phenolic polymer aerogel adsorbent according to solid-liquid ratio of 3:800 (g/mL); placing the conical flask into a constant temperature water bath oscillator, and oscillating at constant temperature (120 rpm) until adsorption separation is balanced; centrifuging (10000 rpm,15 min) and separating, and collecting the phenolic polymer aerogel adsorbent enriched with alkaloids;
c) Adding the phenolic polymer aerogel enriched with the alkaloids into 50 mL methanol eluent containing 1% hydrochloric acid, and stirring at room temperature until complete desorption to obtain a renewable phenolic polymer aerogel adsorbent and an alkaloid eluent; the alkaloid eluent is concentrated by rotary evaporation to obtain high-purity alkaloid extract dry product. The pore size distribution of the phenolic polymer aerogel is 4-6 nm, and the surface potential is-45.36 mV; the adsorption capacity of the alkaloid is 488 mg/g, and the purity of the alkaloid is improved to 90.2%.
FIG. 3 shows the molecular weight (left) and the distribution difference (right) of proteins and polysaccharides in Coptidis rhizoma before and after separation in embodiment 2. As can be seen from the figure, most of non-bioactive macromolecular proteins and polysaccharides in coptis chinensis are removed after the phenolic polymer aerogel is subjected to selective adsorption and separation.
Embodiment 3:
(1) Preparation of phenolic Polymer aerogel
Weighing and weighingAdding resorcinol into deionized water (the mol ratio of resorcinol to deionized water is 3:400), and stirring at room temperature for dissolution; sequentially adding formaldehyde solution (37%) and sodium hydroxide catalyst (the mol ratio of resorcinol to sodium hydroxide is 50:1) into resorcinol solution, and stirring for 15 min to obtain a prepolymerized solution; placing the prepolymerization solution into a reaction kettle, and curing the prepolymerization solution at 100 ℃ for 12 h to obtain phenolic polymer hydrogel; CO after the hydrogel is fully replaced by ethanol 2 Supercritical drying to obtain phenolic polymer aerogel;
(2) Selectively separating alkaloid from the effective components of rhizoma Coptidis:
a) Taking fresh traditional Chinese medicine Huang Lian powder, and dispersing the powder in 40% (v/v) alcohol/water mixed solution according to a solid-to-liquid ratio of 1:30 (g/mL); 50. stirring at a temperature of 1 and h, soaking thoroughly, and then extracting with ultrasound (24 kHz, 240W) for 1 h; centrifuging (10000 rpm,15 min) the suspension after extraction, filtering, and collecting filtrate to obtain Coptidis rhizoma crude extract;
b) Transferring Coptidis rhizoma crude extract into conical flask, and adding phenolic polymer aerogel adsorbent according to solid-liquid ratio of 3:800 (g/mL); placing the conical flask into a constant temperature water bath oscillator, and oscillating at constant temperature (120 rpm) until adsorption separation is balanced; centrifuging (10000 rpm,15 min) and separating, and collecting the phenolic polymer aerogel adsorbent enriched with alkaloids;
c) Adding the phenolic polymer aerogel enriched with the alkaloids into 50 mL methanol eluent containing 1% hydrochloric acid, and stirring at room temperature until complete desorption to obtain a renewable phenolic polymer aerogel adsorbent and an alkaloid eluent; the alkaloid eluent is concentrated by rotary evaporation to obtain high-purity alkaloid extract dry product. The pore size distribution of the phenolic polymer aerogel is 8-10 nm, and the surface potential is-42.382 mV; the adsorption capacity of the alkaloid is 548 mg/g, and the purity of the alkaloid is improved to 80.5%.
Embodiment 4:
(1) Preparation of melamine Polymer aerogel
Sequentially transferring melamine solid, formaldehyde solution (37%) and sodium hydroxide catalyst into deionized water (the molar ratio of melamine to formaldehyde is 1:2, the molar ratio of melamine to deionized water is 9:250, and melamineAnd sodium hydroxide in a molar ratio of 25:1), stirring at 80 ℃ for 30 min to dissolve completely; after the solution is cooled to room temperature, regulating the pH value of the solution to about 3.0 by using concentrated hydrochloric acid, and uniformly stirring to obtain a prepolymerization solution; placing the prepolymerization solution into a reaction kettle, and curing 12 h at 80 ℃ to obtain melamine polymer hydrogel; CO after the hydrogel is fully replaced by ethanol 2 And (5) performing supercritical drying to obtain melamine polymer aerogel.
(2) Selectively separating chlorogenic acid as an active ingredient of the traditional Chinese medicine honeysuckle flower:
a) Pulverizing fresh flos Lonicerae into powder, and dispersing in 10% (v/v) alcohol/water mixed solution at a solid-liquid ratio of 1:30 (g/mL); 50. stirring at a temperature of 1 deg.C and h, soaking, extracting with ultrasound (24 kHz, 240W) for 1 h, centrifuging (10000 rpm,15 min) the suspension after extraction, filtering, and collecting filtrate to obtain flos Lonicerae crude extract;
b) Transferring the crude honeysuckle extract into a conical flask, and adding melamine polymer aerogel adsorbent into the conical flask according to the solid-to-liquid ratio of 3:800 (g/mL); placing the conical flask into a constant temperature water bath oscillator, and oscillating at constant temperature (120 rpm) until adsorption separation is balanced; centrifuging (10000 rpm,15 min) and separating to collect melamine polymer aerogel adsorbent rich in chlorogenic acid;
c) Adding the melamine polymer aerogel enriched with chlorogenic acid into 60% (v/v) ethanol eluent containing 50 mL% hydrochloric acid, and stirring at room temperature until desorption is complete to obtain a renewable melamine polymer aerogel adsorbent and chlorogenic acid eluent; concentrating chlorogenic acid eluent by rotary evaporation to obtain high-purity chlorogenic acid extract dry product. The pore size distribution of the melamine polymer aerogel is 7.5-15.0 nm, and the surface potential is +21.20 mV; chlorogenic acid adsorption capacity is 151 mg/g, and purity of chlorogenic acid is improved to 60.5%.
Fig. 4 is a scanning electron microscope image of the melamine polymer aerogel prepared in this embodiment.
Embodiment 5:
(1) Preparation of melamine Polymer aerogel
Sequentially transferring melamine solid, formaldehyde solution (37%) and sodium hydroxide catalyst into deionized water (the mole ratio of melamine to formaldehyde is 1:3; the mole ratio of melamine to deionized water)The molar ratio is 3:100; the mole ratio of melamine to sodium hydroxide is 20:1), and the melamine and sodium hydroxide are stirred at 80 ℃ for 30 min to be completely dissolved; after the solution is cooled to room temperature, regulating the pH of the solution to about 2.5 by using concentrated hydrochloric acid, and uniformly stirring to obtain a prepolymerization solution; placing the prepolymerization solution into a reaction kettle, and curing 12 h at 80 ℃ to obtain melamine polymer hydrogel; CO after the hydrogel is fully replaced by ethanol 2 And (5) performing supercritical drying to obtain melamine polymer aerogel.
(2) Selectively separating chlorogenic acid as an active ingredient of the traditional Chinese medicine honeysuckle flower:
a) Pulverizing fresh flos Lonicerae into powder, and dispersing in 30% (v/v) alcohol/water mixed solution at a solid-liquid ratio of 1:30 (g/mL); 50. stirring at a temperature of 1 deg.C and h, soaking, extracting with ultrasound (24 kHz, 240W) for 1 h, centrifuging (10000 rpm,15 min) the suspension after extraction, filtering, and collecting filtrate to obtain flos Lonicerae crude extract;
b) Transferring the crude honeysuckle extract into a conical flask, and adding melamine polymer aerogel adsorbent into the conical flask according to the solid-to-liquid ratio of 1:200 (g/mL); placing the conical flask into a constant temperature water bath oscillator, and oscillating at constant temperature (120 rpm) until adsorption separation is balanced; centrifuging (10000 rpm,15 min) and separating to collect melamine polymer aerogel adsorbent rich in chlorogenic acid;
c) Adding the melamine polymer aerogel enriched with chlorogenic acid into 60% (v/v) ethanol eluent containing 50 mL% hydrochloric acid, and stirring at room temperature until desorption is complete to obtain a renewable melamine polymer aerogel adsorbent and chlorogenic acid eluent; concentrating chlorogenic acid eluent by rotary evaporation to obtain high-purity chlorogenic acid extract dry product. The pore size distribution of the melamine polymer aerogel is 10.0-15.0 nm, and the surface potential is +25.42 mV; the chlorogenic acid adsorption capacity is 130 mg/g, and the purity of the chlorogenic acid is improved to 56.5%.
Fig. 5 is a liquid chromatogram of chlorogenic acid of crude extract of honeysuckle before and after separation of melamine polymer aerogel prepared in this embodiment. As can be seen from the figure, the liquid chromatography shows that the relative peak area of chlorogenic acid after separation is significantly improved, i.e. the purity of chlorogenic acid is increased.
Embodiment 6:
(1) Preparation of melamine Polymer aerogel
Sequentially transferring melamine solid, formaldehyde solution (37%) and sodium hydroxide catalyst into deionized water (the molar ratio of melamine to formaldehyde is 1:4, the molar ratio of melamine to deionized water is 3:100, the molar ratio of melamine to sodium hydroxide is 40:1), and stirring at 80 ℃ for 30 min to dissolve completely; after the solution is cooled to room temperature, regulating the pH of the solution to about 1.5 by using concentrated hydrochloric acid, and uniformly stirring to obtain a prepolymerization solution; placing the prepolymerization solution into a reaction kettle, and curing 12 h at 80 ℃ to obtain melamine polymer hydrogel; CO after the hydrogel is fully replaced by ethanol 2 And (5) performing supercritical drying to obtain melamine polymer aerogel.
(2) Selectively separating chlorogenic acid as an active ingredient of the traditional Chinese medicine honeysuckle flower:
a) Pulverizing fresh flos Lonicerae into powder, and dispersing in 50% (v/v) alcohol/water mixed solution at a solid-liquid ratio of 1:30 (g/mL); 50. stirring at a temperature of 1 deg.C and h, soaking, extracting with ultrasound (24 kHz, 240W) for 1 h, centrifuging (10000 rpm,15 min) the suspension after extraction, filtering, and collecting filtrate to obtain flos Lonicerae crude extract;
b) Transferring the crude honeysuckle extract into a conical flask, and adding melamine polymer aerogel adsorbent into the conical flask according to the solid-to-liquid ratio of 1:150 (g/mL); placing the conical flask into a constant temperature water bath oscillator, and oscillating at constant temperature (120 rpm) until adsorption separation is balanced; centrifuging (10000 rpm,15 min) and separating to collect melamine polymer aerogel adsorbent rich in chlorogenic acid;
c) Adding the melamine polymer aerogel enriched with chlorogenic acid into 60% (v/v) ethanol eluent containing 50 mL% hydrochloric acid, and stirring at room temperature until desorption is complete to obtain a renewable melamine polymer aerogel adsorbent and chlorogenic acid eluent; concentrating chlorogenic acid eluent by rotary evaporation to obtain high-purity chlorogenic acid extract dry product. The pore size distribution of the melamine polymer aerogel is 6.0-10.0 nm, and the surface potential is +18.94 mV; chlorogenic acid adsorption capacity is 106 mg/g, and purity of chlorogenic acid is improved to 50.8%.
The foregoing embodiments are merely illustrative of the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement the same, not to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (10)
1. An organic polymer aerogel for separating active components of traditional Chinese medicine and a preparation method thereof are characterized by comprising the following steps:
step one, preparing organic polymer aerogel:
adding ammonia organic compound and aldehyde organic compound reaction monomer into a certain amount of deionized water, dissolving completely, homogenizing, adding catalyst, and stirring to obtain prepolymerized solution; hydrochloric acid or sodium hydroxide is used for regulating the pH value of the pre-polymerized solution, then the pre-polymerized solution is put into a reaction kettle for sealing, and a sol-gel process of polycondensation reaction is carried out under the conditions of high temperature and high pressure to obtain the organic polymer hydrogel; fully replacing the organic polymer hydrogel with ethanol, and drying to obtain organic polymer aerogel;
or adding a phenolic organic compound and an aldehyde organic compound reaction monomer into a certain amount of deionized water, dissolving completely and homogenizing, adding a catalyst, stirring to obtain a prepolymerization solution, placing the prepolymerization solution into a reaction kettle for sealing, and performing a sol-gel process of polycondensation reaction under high temperature and high pressure to obtain the organic polymer hydrogel; fully replacing the organic polymer hydrogel with ethanol, and drying to obtain organic polymer aerogel;
step two, selectively separating active components of the traditional Chinese medicine:
s1, pulverizing fresh traditional Chinese medicines, dispersing into an alcohol/water mixed solution, stirring, carrying out ultrasonic treatment, centrifuging, and collecting supernatant to obtain a crude traditional Chinese medicine extract;
s2, placing the organic polymer aerogel serving as an adsorbent into a crude traditional Chinese medicine extracting solution for adsorption, oscillating at constant temperature, and centrifuging to obtain aerogel enriched with active components;
s3, placing the aerogel enriched with the active components in an eluent, and stirring at room temperature until desorption is complete to obtain a renewable aerogel adsorbent and a traditional Chinese medicine active component eluent; the eluent of the active components of the traditional Chinese medicine is concentrated by rotary evaporation to obtain a high-purity dry extract of the active components of the traditional Chinese medicine.
2. The organic polymer aerogel for separating active components of traditional Chinese medicine according to claim 1 and the preparation method thereof, wherein the organic polymer aerogel is characterized in that: in the first step, the molar ratio of the ammonia organic compound to the aldehyde organic compound is 1:2-6;
and/or, in the first step, the overall concentration of the ammonia organic compound is 0.5-2 mol/L;
and/or in the first step, the molar ratio of the ammonia organic compound to the catalyst is 10-100:1;
and/or, in the first step, hydrochloric acid or sodium hydroxide adjusts the pH value of the pre-polymerization solution to 1.5-3.0;
and/or, in the first step, when the ammonia organic compound and the aldehyde organic compound react, the specific conditions of the reaction are as follows: the reaction temperature is 60-120 ℃, and the reaction time is 8-12 h.
3. The organic polymer aerogel for separating active components of traditional Chinese medicine according to claim 1 and the preparation method thereof, wherein the organic polymer aerogel is characterized in that: in the first step, the molar ratio of the phenolic organic compound to the aldehyde organic compound is 1:3-5;
and/or, in the first step, the total concentration of the phenolic organic compound is 0.5-2 mol/L;
and/or in the first step, the molar ratio of the phenolic organic compound to the catalyst is 5-500:1;
and/or, in the first step, when the phenolic organic compound is reacted with the aldehyde organic compound, the specific conditions of the reaction are as follows: the reaction temperature is 100-180 ℃ and the reaction time is 10-14 h.
4. The organic polymer aerogel for separating active components of traditional Chinese medicine according to claim 1 and the preparation method thereof, wherein the organic polymer aerogel is characterized in that: in the first step, the specific conditions of the drying are as follows: CO at 60-80 ℃ and 10-15 MPa 2 And (5) supercritical drying.
5. The organic polymer aerogel for separating active components of traditional Chinese medicine according to claim 1 and the preparation method thereof, wherein the organic polymer aerogel is characterized in that: in the second step S1, the traditional Chinese medicine is a Chinese herbal medicine source with the active ingredient of alkaloid or a Chinese herbal medicine source with the active ingredient of chlorogenic acid.
6. The organic polymer aerogel for separating active components of traditional Chinese medicine according to claim 5 and the preparation method thereof, wherein the organic polymer aerogel is characterized in that: the Chinese herbal medicine source with alkaloid as the effective component is coptis chinensis, epimedium herb and poppy;
and/or the Chinese herbal medicine sources with chlorogenic acid as the active ingredients are honeysuckle, jerusalem artichoke and eucommia ulmoides leaves.
7. The organic polymer aerogel for separating active components of traditional Chinese medicine according to claim 1 and the preparation method thereof, wherein the organic polymer aerogel is characterized in that: in the second step S1, the alcohol/water mixed solution is an ethanol water solution with the volume fraction of 10-90%.
8. The organic polymer aerogel for separating active components of traditional Chinese medicine according to claim 1 and the preparation method thereof, wherein the organic polymer aerogel is characterized in that: in the second step S2, specific conditions of the adsorption are as follows:
the solid-liquid ratio of the adsorbent to the crude extract of the traditional Chinese medicine is 1 g:100-500 mL, the adsorption pH is 3.0-11.0, the adsorption temperature is 20-80 ℃, and the adsorption time is 1-6 h.
9. The organic polymer aerogel for separating active components of traditional Chinese medicine according to claim 1 and the preparation method thereof, wherein the organic polymer aerogel is characterized in that: in the second step S3, the eluent is one or more of ethanol, methanol, hydrochloric acid and deionized water;
and/or in the second step S3, the volume of the eluent is 0.5-5 times of the volume of the crude extract of the traditional Chinese medicine in the second step S2.
10. The organic polymer aerogel for separation of active components of traditional Chinese medicine according to any one of claims 1 to 9, and its preparation method, characterized in that: in the second step S1, the specific condition of centrifugation is 10000-11000 rpm for 10-15 min;
and/or in the second step S1, the specific condition of stirring is that stirring is carried out at 50-70 ℃ for 1-2 h.
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| US5081163A (en) * | 1991-04-11 | 1992-01-14 | The United States Of America As Represented By The Department Of Energy | Melamine-formaldehyde aerogels |
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| US5081163A (en) * | 1991-04-11 | 1992-01-14 | The United States Of America As Represented By The Department Of Energy | Melamine-formaldehyde aerogels |
| CN110467742A (en) * | 2019-08-30 | 2019-11-19 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of phenolic aldehyde aeroge |
| CN114452951A (en) * | 2021-12-15 | 2022-05-10 | 淮阴工学院 | Phenolic aerogel rubidium/cesium special-effect adsorbent and preparation method and application thereof |
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