CN111393487B - Preparation method of polymorphic fulvic acid nano material - Google Patents
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Abstract
The invention relates to the field of preparation of fulvic acid nano materials, in particular to a preparation method of a polymorphic fulvic acid nano material. Firstly, mixing coal sample powder and potassium hydroxide, adding distilled water, stirring, heating and refluxing, then cooling reaction liquid to room temperature, centrifuging and collecting first supernatant; dropwise adding dilute sulfuric acid into the first supernatant, standing for precipitation, and separating and extracting a second supernatant; adding a hydrogen peroxide solution into the second supernatant, oxidizing the second supernatant under the action of a metal catalyst, and centrifuging the reaction liquid to remove the metal catalyst to obtain a third supernatant; purifying the third supernatant for multiple times by using macroporous resin and hydrogen ion exchange resin to obtain a fulvic acid solution; and (3) freeze-drying the fulvic acid solution to obtain the polymorphic fulvic acid nano material with high crystallinity. The fulvic acid nano material has high crystallinity and clear lattice stripes, and the interface spacing is 0.26 nm, 0.28 nm, 0.30 nm and 0.31 nm.
Description
Technical Field
The invention relates to the field of preparation of fulvic acid nano materials, in particular to a preparation method of a polymorphic fulvic acid nano material.
Background
Humic acid is a natural organic macromolecular mixture and has extremely wide application in the fields of industry, agriculture, medicine and the like. Fulvic acid is the component of humic acid with the smallest molecular weight, the lightest color, water solubility and no cytotoxicity.
Humic acid is an organic compound with a complex structure obtained by extracting, separating and purifying grass peat, lignite, weathered coal and the like, and the composition structure of the humic acid is not completely clear so far. Known humic acid molecules contain benzene rings, condensed rings and certain heterocycles (such as pyrrole, furan, indole and the like), wherein aromatic rings are connected by bridges, and the aromatic rings have various functional groups, mainly carboxyl, phenolic hydroxyl, methoxy, quinonyl and the like. Due to such a complex molecular structure of humic acid, it is possible to exhibit various physicochemical properties. For example, humic acid itself has a large molecular weight and can be associated into larger particles in a certain medium, thus having colloidal properties and adsorption capacity; humic acid molecules have a plurality of carboxyl groups and phenolic hydroxyl groups, so the humic acid has weak acidity and has stronger ion exchange capacity, chelating capacity and buffering capacity; the phenol and quinone structures on humic acid molecules may participate in the electron transfer system of biological oxidation reduction. These physicochemical properties may also affect the function of the biomacromolecule, thereby leading to physiological and pharmacological activities.
Humic acid is weakly acidic and is classified into humic acid black, humic acid brown and humic acid yellow according to their solubility and color in different solvents. Wherein the part which is only soluble in alkali is called black humic acid, the part which is soluble in acetone or ethanol is called brown humic acid, and the part which is soluble in water is called yellow humic acid.
The Chinese Ming dynasty Li Shizhen Ben Cao gang mu has records: (Shi Tan) (i.e. Fengshi coal) is mainly used for treating qi and blood pain and traumatic hemorrhage of women; the benorite is mainly used for treating menstrual accumulation and blood clots of women and treating nose flood and hematemesis; [ Chengdong Huumu ], a rotten part of Chengdong ancient wood in the soil. The medicine has salty taste, warm nature and no toxicity, and is suitable for treating cardiac and abdominal pain, diarrhea, and purulent blood in stool. For centipede bites, the wood-rotting liquid is applied, or ground into powder and applied with vinegar. If the hands and feet are painful and not red, rotten wood is used for cooking soup. Heat-affected areas, especially those with pain. The "Chengdong rotten wood" is the grass peat. For instance, it is also recorded in the book Fang from Zheng Zhi Zhun Cao Yan Yi (Standard rope and ulcer treatment for syndrome of disease) 'Jinwu san' for treating testicular carbuncle and sore. The flour charcoal in the formula is also one of grass carbon. The medical scientist confirms that the stone charcoal, the white good soil, the Chengdong humic acid, the Zijin dew and the like can be all substances containing humic acid. According to the modern chemical engineering process theory, the humic acid wood stain juice is the humic acid which is a component with pharmacological action described in the compendium of the highest biological substance in humic acid substances.
Fulvic acid is used in modern medicine to start with a peat bath. It is most commonly used for adjuvant treatment of osteoarticular diseases such as rheumatism and rheumatoid arthritis, and also for treatment of chronic skin diseases (eczema, dermatitis, etc.) and gynecological diseases (vulvitis, menstrual disorder, etc.). The subsequent series of researches find that fulvic acid is the main effective component in the peat bath. The research around the medical science of fulvic acid at home and abroad does a great deal of work in the aspects of basic research work such as physiology, pharmacological activity, toxicity and the like or clinical curative effect observation. Experimental results prove that the fulvic acid has an anti-tumor effect. Fullwu reports that Lianjiang humic acid and Turpan humic acid have moderate inhibition effect on S180 and liver cancer of mice; the pharmaceutical research institute of Chinese academy of medicine reports that the Schlemm' S fulvic acid has tumor inhibiting effect on S180, L615, Lewis lung cancer and W256 rat tumor strains; according to the history of the Zhangzhou bath, the administration is started 3 days before tumor inoculation, the tumor inhibition rate of S37 reaches 44.2%, and the Zhangyu bath also has a certain inhibition effect on B16 and L615; vetvicka and the like use fulvic acid extracted from Czech weathered lignite and Chinese lignite to treat BALB/c nude mouse Ptas64 breast cancer animal models through intraperitoneal injection, find that both the fulvic acid and the fulvic acid can affect humoral immunity and cellular immunity, and in addition, Vetvicka also analyzes 5 fulvic acids produced in the United states, and finds that the fulvic acid can stimulate immune response and reduce tumor body weight through oral administration to treat Lewis lung cancer mouse models. Jayasooriya et al report that fulvic acid can enhance the activity of mouse mononuclear macrophage leukemia cell RAW264.7 nuclear factor NF-kB, and human liver cancer cell Hep3B, human prostate cancer cell LNCaP and human promyelocytic leukemia cell HL-60 all show the death phenomenon of tumor cells, and speculate that fulvic acid can possibly play a cell killing effect by stimulating the generation of immune regulatory molecule NO. In folk, the patient with serious tumor takes fulvic acid, and the tumor is reduced and recovered. The case of using fulvic acid to cure tumor patients was discussed by physicians in hami city, autonomous region of Xinjiang and physicians in Hozhou city, Shanxi province with the same applicant. The inventor visits peat institute in 2009, russian stokes city.
Fulvic acid is an assembly of molecules with cluster character and nanometer size. The fulvic acid can be combined with the anti-cancer drug through the hydrogen bond effect, and the anti-cancer drug is wrapped in the cavity of the fulvic acid, so that the fulvic acid can be used as a targeted anti-cancer drug. Then the target anticancer drug is combined with the specific receptor on the surface of the tumor cell and enters the tumor cell under the endocytosis of the tumor cell, thereby realizing effective target anticancer treatment.
The fulvic acid is used as a carrier of the anticancer drug and has the following advantages: firstly, fulvic acid as a hydrophilic biopolymer nanoparticle can be absorbed across a membrane through endocytosis of the cell membrane. Therefore, the fulvic acid can be taken as a carrier for encapsulating the anti-cancer drug and is endocytosed by the tumor cells so as to enter the tumor cells. And secondly, the fulvic acid has better pharmacological action and can exert the killing effect of tumor cells, and the fulvic acid can play a synergistic effect with the anti-cancer drugs, so that the curative effect of the drugs is improved. And the fulvic acid has good biocompatibility, no cytotoxicity and no toxic or side effect on other non-target tissues, and the fulvic acid wraps the anticancer drug in the cavity, so that the toxic or side effect of the anticancer drug on other non-target tissues is further reduced.
At present, the prior art is used for the killing of inflammation and tumor cells according to the pharmacological action of fulvic acid. But the fulvic acid nano material with a polymorphic structure is not prepared and characterized in the prior art. The natural organic macromolecular mixture cannot obtain single crystals with proper size and size, and the powder X-ray diffraction technology (Xrd) is an effective means for determining powder crystal materials. The invention prepares the polymorphic fulvic acid nano material with high crystallinity for the first time by using coal as a raw material. In addition, the present invention is characterized by Transmission Electron Microscopy (TEM) techniques.
Disclosure of Invention
The invention aims to provide a preparation method of a polymorphic fulvic acid nano material with high crystallinity.
The invention is realized by the following technical scheme: a preparation method of a polymorphic fulvic acid nano material with high crystallinity comprises the following steps:
1) carrying out alkali treatment on the coal sample:
firstly, grinding a coal sample into powder, then mixing the coal sample powder with potassium hydroxide, adding distilled water, stirring and heating and refluxing for 8-10h at 50 ℃, then cooling a reaction solution to room temperature, and centrifuging to collect a first supernatant;
2) adding acid for precipitation:
dropwise adding dilute sulfuric acid into the first supernatant, adjusting the pH of the first supernatant to 1-5, standing for precipitation, and separating and extracting a second supernatant;
3) oxidizing the second supernatant:
adding a hydrogen peroxide solution into the second supernatant, oxidizing the second supernatant under the action of a metal catalyst, and centrifuging the reaction liquid to remove the metal catalyst to obtain a third supernatant;
4) purifying the third supernatant:
purifying the third supernatant for multiple times by using macroporous resin and hydrogen ion exchange resin to obtain a fulvic acid solution;
5) freeze drying to obtain fulvic acid nano material
And (3) freeze-drying the fulvic acid solution to obtain the polymorphic fulvic acid nano material with high crystallinity.
As a further improvement of the technical scheme of the invention, the centrifugation parameters in the step 1) and the step 3) are rotation speed centrifugation of 3600r/min for 20 min.
As a further improvement of the technical scheme of the invention, the concentration of the hydrogen peroxide solution is 15-28 wt%.
As a further improvement of the technical scheme of the invention, the metal catalyst is a zinc-iron mixed metal catalyst.
As a further improvement of the technical scheme of the invention, in the step 4), the purification times are 5 times.
As a further improvement of the technical scheme of the invention, the coal sample is weathered coal or lignite.
As a further improvement of the technical scheme of the invention, the particle size of the coal sample powder is 80-200 meshes.
The preparation method can prepare and obtain the polymorphic fulvic acid nano material with high crystallinity, the fulvic acid nano material has high crystallinity and clear lattice stripes, and the interface spacing is 0.26 nm, 0.28 nm, 0.30 nm and 0.31 nm.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIGS. 1 to 3 are high-power transmission (HR-TEM) photographs of fulvic acid nanomaterials obtained from example 1. As can be seen from fig. 1, 2 and 3, the fulvic acid nanomaterial has an irregular morphology. The HR-TEM images of fig. 2 and 3 show clear lattice fringes with interfacial spacings of 0.26, 0.28, 0.30 and 0.31 nm, indicating that the nanocrystals have high crystallinity. There is a Selected Area Electron Diffraction (SAED) mode in fig. 2 and 3. Different diffraction rings are shown in fig. 2 and 3, indicating that the fulvic acid nanomaterial has a fine polycrystalline structure.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The technical solution of the present invention will be described in detail by the following specific examples.
Example 1
A preparation method of a polymorphic fulvic acid nano material with high crystallinity comprises the following steps:
1) carrying out alkali treatment on the coal sample:
and (3) carrying out alkali treatment on the coal sample. Firstly, grinding a coal sample into powder, then weighing 100.00g of the coal sample and 10.00g of potassium hydroxide in a three-neck flask, adding 1000 mL of distilled water, stirring by using an electromagnetic stirrer at 50 ℃, heating and refluxing for 8 h, then cooling the reaction liquid to room temperature, centrifuging at the rotating speed of 3600r/min for 20min, and collecting a first supernatant;
2) adding acid for precipitation:
dropwise adding 5wt% of dilute sulfuric acid into the first supernatant, adjusting the pH of the first supernatant to 3, standing and precipitating for 7h, and separating and extracting a second supernatant which is yellow;
3) oxidizing the second supernatant:
adding 20wt% of hydrogen peroxide solution into the second supernatant, oxidizing the second supernatant for 3h under the action of a zinc-iron mixed metal catalyst, centrifuging the reaction solution at a rotating speed of 3600r/min for 20min, and removing the metal catalyst to obtain a third supernatant;
4) purifying the third supernatant:
purifying the third supernatant liquid for 5 times by using macroporous resin and hydrogen ion exchange resin to obtain a fulvic acid solution with the concentration of 95 wt%;
5) freeze drying to obtain fulvic acid nano material
And (3) freeze-drying the fulvic acid solution to obtain the polymorphic fulvic acid nano material with high crystallinity.
In this embodiment, the preparation method of the zinc-iron mixed metal catalyst is as follows: uniformly dispersing polyvinylpyrrolidone (PVP) into an ethanol solvent by ultrasonic. After uniform dispersion, under the condition of magnetic stirring, a mixed solution of zinc nitrate and ferric nitrate is added dropwise, and then a sodium borohydride ethanol solution is added. And standing after uniform mixing, centrifuging, washing and drying to obtain the zinc-iron mixed metal catalyst.
Example 2
A preparation method of a polymorphic fulvic acid nano material with high crystallinity comprises the following steps:
1) carrying out alkali treatment on the coal sample:
and (3) carrying out alkali treatment on the coal sample. Firstly, grinding a coal sample into powder, then weighing 100.00g of the coal sample and 10.00g of potassium hydroxide in a three-neck flask, adding 1000 mL of distilled water, stirring by using an electromagnetic stirrer at 50 ℃, heating and refluxing for 9 h, then cooling the reaction liquid to room temperature, centrifuging at the rotating speed of 3600r/min for 20min, and collecting a first supernatant;
2) adding acid for precipitation:
dropwise adding 10wt% of dilute sulfuric acid into the first supernatant, adjusting the pH of the first supernatant to 1, standing and precipitating for 7 hours, and separating and extracting a second supernatant, wherein the second supernatant is yellow;
3) oxidizing the second supernatant:
adding 15wt% of hydrogen peroxide solution into the second supernatant, oxidizing the second supernatant for 3h under the action of a zinc-iron mixed metal catalyst, centrifuging the reaction solution at a rotating speed of 3600r/min for 20min, and removing the metal catalyst to obtain a third supernatant;
4) purifying the third supernatant:
purifying the third supernatant liquid for 5 times by using macroporous resin and hydrogen ion exchange resin to obtain a fulvic acid solution with the concentration of 95 wt%;
5) freeze drying to obtain fulvic acid nano material
And (3) freeze-drying the fulvic acid solution to obtain the polymorphic fulvic acid nano material with high crystallinity.
In this example, a zinc-iron mixed metal catalyst was prepared in the same manner as in example 1.
Example 3
A preparation method of a polymorphic fulvic acid nano material with high crystallinity comprises the following steps:
1) carrying out alkali treatment on the coal sample:
and (3) carrying out alkali treatment on the coal sample. Firstly, grinding a coal sample into powder, then weighing 100.00g of the coal sample and 10.00g of potassium hydroxide in a three-neck flask, adding 1000 mL of distilled water, stirring by using an electromagnetic stirrer at 50 ℃, heating and refluxing for 10h, then cooling the reaction liquid to room temperature, centrifuging at the rotating speed of 3600r/min for 20min, and collecting a first supernatant;
2) adding acid for precipitation:
dropwise adding 2wt% of dilute sulfuric acid into the first supernatant, adjusting the pH of the first supernatant to 5, standing and precipitating for 7 hours, and separating and extracting a second supernatant, wherein the second supernatant is yellow;
3) oxidizing the second supernatant:
adding a 28wt% hydrogen peroxide solution into the second supernatant, oxidizing the second supernatant for 3h under the action of a zinc-iron mixed metal catalyst, centrifuging the reaction solution at a rotating speed of 3600r/min for 20min, and removing the metal catalyst to obtain a third supernatant;
4) purifying the third supernatant:
purifying the third supernatant liquid for 5 times by using macroporous resin and hydrogen ion exchange resin to obtain a fulvic acid solution with the concentration of 96 wt%;
5) freeze drying to obtain fulvic acid nano material
And (3) freeze-drying the fulvic acid solution to obtain the polymorphic fulvic acid nano material with high crystallinity.
In this example, a zinc-iron mixed metal catalyst was prepared in the same manner as in example 1.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (5)
1. A preparation method of a polymorphic fulvic acid nano material with high crystallinity is characterized by comprising the following steps:
1) carrying out alkali treatment on the coal sample:
firstly, grinding a coal sample into powder, then mixing the coal sample powder with potassium hydroxide, adding distilled water, stirring and heating and refluxing for 8-10h at 50 ℃, then cooling a reaction solution to room temperature, and centrifuging to collect a first supernatant;
2) adding acid for precipitation:
dropwise adding dilute sulfuric acid into the first supernatant, adjusting the pH of the first supernatant to 1-5, standing for precipitation, and separating and extracting a second supernatant;
3) oxidizing the second supernatant:
adding hydrogen peroxide solution into the second supernatant, oxidizing the second supernatant under the action of a metal catalyst, wherein the concentration of the hydrogen peroxide solution is 15-28wt%,
then centrifuging the reaction liquid to remove the metal catalyst to obtain a third supernatant;
wherein the metal catalyst is a zinc-iron mixed metal catalyst, and the zinc-iron mixed metal catalyst is prepared by the following method: uniformly dispersing polyvinylpyrrolidone (PVP) into an ethanol solvent by ultrasonic; after uniform dispersion, dropwise adding a mixed solution of zinc nitrate and ferric nitrate under the condition of magnetic stirring, and then adding a sodium borohydride ethanol solution; uniformly mixing, standing, centrifuging, washing and drying to obtain a zinc-iron mixed metal catalyst;
4) purifying the third supernatant:
purifying the third supernatant for multiple times by using macroporous resin and hydrogen ion exchange resin to obtain a fulvic acid solution;
5) freeze drying to obtain fulvic acid nano material
And (3) freeze-drying the fulvic acid solution to obtain the polymorphic fulvic acid nano material with high crystallinity.
2. The method for preparing the polymorphic fulvic acid nanomaterial with high crystallinity according to claim 1, wherein the centrifugation parameters in step 1) and step 3) are 3600r/min for 20 min.
3. The method for preparing the fulvic acid nanomaterial with a high-crystallinity polymorphic form according to claim 1 or 2, wherein in the step 4), the number of purification times is 5.
4. The method for preparing the polymorphic fulvic acid nanomaterial with high crystallinity according to claim 1 or 2, wherein the coal sample is weathered coal or lignite.
5. The method for preparing a polymorphic fulvic acid nanomaterial with high crystallinity according to claim 1 or 2, wherein the particle size of the coal-like powder is 80-200 mesh.
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Effective date of registration: 20211103 Address after: 030619 No. 319, University street, Wujinshan Town, Yuci District, Jinzhong City, Shanxi Province Applicant after: TAIYUAN NORMAL University Applicant after: Shanxi Yicheng Hongye humic acid Technology Co., Ltd Address before: 030619 No. 319, University street, Wujinshan Town, Yuci District, Jinzhong City, Shanxi Province Applicant before: TAIYUAN NORMAL University Applicant before: Shanxi Yicheng Hongye humic acid Technology Co., Ltd Applicant before: Shanxi Branch of China coal mining First Exploration Bureau Co.,Ltd. |
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