CN113461045A - Method for preparing virus-like hollow mesoporous copper oxide nanoparticles - Google Patents

Method for preparing virus-like hollow mesoporous copper oxide nanoparticles Download PDF

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Publication number
CN113461045A
CN113461045A CN202110758967.6A CN202110758967A CN113461045A CN 113461045 A CN113461045 A CN 113461045A CN 202110758967 A CN202110758967 A CN 202110758967A CN 113461045 A CN113461045 A CN 113461045A
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virus
copper oxide
stirring
silicon oxide
ethanol
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刘小龙
王培园
密夫山
杨英祥
陈三妹
王昌华
刘明峰
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Fujian Chenrun Biotech Co ltd
Xiamen Institute of Rare Earth Materials
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Fujian Chenrun Biotech Co ltd
Xiamen Institute of Rare Earth Materials
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    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00Compounds of copper
    • C01G3/02Oxides; Hydroxides

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Abstract

The invention discloses a method for manufacturing virus-like hollow mesoporous copper oxide nanoparticles, which comprises the steps of taking copper oxide coated virus-like mesoporous silicon dioxide nanoparticles as a template, adopting a growth mode of epitaxial single micelles in a cyclohexane-water two-phase reaction system, taking hexadecyl trimethyl ammonium bromide as a surfactant, using triethanolamine in a weak alkaline environment, carrying out hydrolysis assembly to form monodisperse virus-like mesoporous silicon oxide particles by gently stirring tetraethyl orthosilicate, taking the particles as the template, taking hexamethylene tetramine as a reducing agent, facilitating the adhesion and hydrolytic nucleation of a copper nitrate precursor on the rough surface of the monodisperse virus silicon oxide nanoparticles, forming a rough surface structure similar to virus spike protein, and finally etching and removing the silicon oxide template in an alkaline solution to obtain the virus-like hollow mesoporous copper oxide nanoparticles; the method can quickly and efficiently finish the preparation of the viroid hollow mesoporous copper oxide nano particles.

Description

Method for preparing virus-like hollow mesoporous copper oxide nanoparticles
Technical Field
The invention belongs to the technical field of processing of medical copper oxide raw materials, and particularly relates to a method for manufacturing viroid hollow mesoporous copper oxide nanoparticles.
Background
Copper ions are trace elements of organisms and participate in activities of various enzymes related to oxidative stress, medical copper oxide is widely applied in the aspect of medical treatment, but virus-like hollow mesoporous copper oxide nanoparticles serving as a raw material of the medical copper oxide are not prepared by a mature and green method, and the application development of the medical copper oxide is restricted.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for manufacturing viroid hollow mesoporous copper oxide nanoparticles.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for preparing virus-like hollow mesoporous copper oxide nanoparticles comprises the following steps:
step 1, adding 1-5 g of hexadecyl trimethyl ammonium bromide and 0.18-0.8 g of triethanolamine into a 100 ml single-neck round-bottom flask, then adding 50-70 ml of water, controlling the temperature of an oil bath at 50-70 ℃, and stirring for 55-70 min with mild.
Step 2, after stirring, dropwise adding 15-25 ml of cyclohexane solution to the upper layer of hexadecyl trimethyl ammonium bromide aqueous solution in a single-mouth original bottom flask, wherein the cyclohexane solution contains 20 volume percent tetraethyl orthosilicate, keeping the oil bath temperature at 50-70 ℃, and stirring for 11-13 h; cetyl trimethyl ammonium bromide is used as a surfactant, and tetraethyl orthosilicate can be hydrolyzed and assembled into monodisperse virus-like mesoporous silica particles in a weak alkaline environment by triethanolamine.
And 3, after the reaction is finished, taking the aqueous phase for centrifugation, washing the aqueous phase and the ethanol for three times respectively, dispersing the aqueous phase and the ethanol into 50ml of ethanol solution, carrying out reflux extraction on the surfactant cetyl trimethyl ammonium bromide at the oil bath temperature of 55-65 ℃, repeatedly extracting for 3 times, and extracting for 12 hours each time to obtain the monodisperse virus silicon oxide nanoparticles.
Step 4, ultrasonically dispersing 100 mg of monodisperse virus silicon oxide nano particles into 50ml of deionized water, and then adding 0.123g of Cu (NO)3)2•3H2And O, stirring in an oil bath at the temperature of 85-95 ℃ for 30-45 min, and controlling the rotation speed at 550-650 rpm.
Step 5, after stirring, adding 0.09g of hexamethylenetetramine into the solution obtained in the step 4, continuously stirring and reacting for 110-120 min, after the reaction is finished, centrifugally separating and collecting a product, and washing with water and ethanol for three times respectively; by using hexamethylenetetramine as a reducing agent, the rough surface of the monodisperse virus silicon oxide nano particles is beneficial to the adhesion and hydrolysis nucleation of a copper nitrate precursor, so that the appearance of the virus-like mesoporous silicon oxide can be copied, and a rough surface structure similar to virus spike protein is formed.
And 6, etching in an alkaline solution to remove the silicon oxide template.
Preferably, the ethanol solution in the step 3 contains 60% by mass of ammonium nitrate.
Preferably, the removing of the silicon oxide template in step 6 comprises the following steps: dispersing the product into 0.1M NaOH aqueous solution, etching to remove the silicon oxide template, placing in a 60 ℃ oven for 24 hours, washing with ethanol for three times respectively to obtain the final product viroid hollow mesoporous copper oxide nanoparticles.
Compared with the prior art, the invention has the beneficial effects that:
1) the method can rapidly, efficiently and greenly finish the preparation of the viroid hollow mesoporous copper oxide nanoparticles, fills the blank in the preparation of the viroid hollow mesoporous copper oxide nanoparticles, and ensures that the medical copper oxide is not limited by the supply of raw materials in the development process.
2) The virus-like mesoporous silica nano-particle coated with copper oxide is used as a template, and the growth mode of an epitaxial single micelle is adopted in a cyclohexane-water two-phase reaction system, cetyl trimethyl ammonium bromide is used as a surfactant, triethanolamine is in a weak alkaline environment, can be hydrolyzed and assembled into monodisperse viroid mesoporous silica particles by mildly stirring tetraethyl orthosilicate, then the particles are used as a template, hexamethylenetetramine is used as a reducing agent, the rough surface of the monodisperse virus silicon oxide nano particles is beneficial to the adhesion and hydrolytic nucleation of a copper nitrate precursor, so that the appearance of the viroid mesoporous silicon oxide can be copied, a rough surface structure similar to the virus spike protein is formed, finally the silicon oxide template is removed by etching in an alkaline solution, in the manufacturing process, the process is simple and easy to operate, and the method is green and environment-friendly and does not pollute the environment.
Drawings
FIG. 1 is a schematic view of a viroid mesoporous silica in the method for preparing the viroid hollow mesoporous copper oxide nanoparticles of the present invention.
FIG. 2 is a schematic view of a viroid mesoporous silica coated with copper oxide in the method for preparing the viroid hollow mesoporous copper oxide nanoparticles of the present invention.
FIG. 3 is a schematic view of the viroid hollow mesoporous copper oxide nanoparticles prepared by the method of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to fig. 1 to 3 in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and all other embodiments obtained by a person of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
Example 1:
a method for preparing virus-like hollow mesoporous copper oxide nanoparticles comprises the following steps:
step 1, adding 1g of hexadecyl trimethyl ammonium bromide and 0.18g of triethanolamine into a 100 ml single-neck round-bottom flask, then adding 60ml of water, controlling the temperature of an oil bath at 60 ℃, and stirring for 60min gently.
Step 2, after stirring, dropwise adding 20ml of 20 volume percent tetraethyl orthosilicate cyclohexane solution on the upper layer of the hexadecyl trimethyl ammonium bromide aqueous solution in the single-neck original bottom flask, keeping the oil bath temperature at 60 ℃, and stirring for reaction for 12 hours; cetyl trimethyl ammonium bromide is used as a surfactant, and tetraethyl orthosilicate can be hydrolyzed and assembled into monodisperse virus-like mesoporous silica particles in a weak alkaline environment by triethanolamine.
And 3, after the reaction is finished, taking the aqueous phase for centrifugation, washing the aqueous phase and the ethanol for three times respectively, dispersing the aqueous phase and the ethanol into 50ml of ethanol solution containing 60 mass percent ammonium nitrate, carrying out reflux extraction on the surfactant cetyl trimethyl ammonium bromide at the oil bath temperature of 60 ℃, repeatedly extracting for 3 times, and extracting for 12 hours each time to obtain the monodisperse virus silicon oxide nanoparticles.
Step 4, ultrasonically dispersing 100 mg of monodisperse virus silicon oxide nano particles into 50ml of deionized water, and then adding 0.123g of Cu (NO)3)2•3H2And O, stirring in an oil bath at 90 ℃ for 30min, and controlling the rotation speed at 600 rpm.
Step 5, after stirring, adding 0.09g of hexamethylenetetramine into the solution obtained in the step 4, continuously stirring for reacting for 110min, after the reaction is finished, centrifugally separating and collecting a product, and washing the product with water and ethanol for three times respectively; in aqueous solution, hexamethylenetetramine is used as a reducing agent, and the rough surface of the monodisperse virus silicon oxide nano particles is beneficial to the adhesion and hydrolysis nucleation of a copper nitrate precursor, so that the appearance of the virus-like mesoporous silicon oxide can be copied, and a rough surface structure similar to virus spike protein is formed.
And 6, etching and removing the silicon oxide template in an alkaline solution, dispersing the product into a 0.1M NaOH aqueous solution, etching and removing the silicon oxide template, placing the product in a 60 ℃ oven for 24 hours, and washing ethanol with water for three times respectively to obtain the final product viroid hollow mesoporous copper oxide nano particle.
Example 2:
a method for preparing virus-like hollow mesoporous copper oxide nanoparticles comprises the following steps:
step 1, adding 1g of hexadecyl trimethyl ammonium bromide and 0.35g of triethanolamine into a 100 ml single-neck round-bottom flask, then adding 65ml of water, controlling the temperature of an oil bath to be 65 ℃, and stirring for 65min gently.
Step 2, after stirring, dropwise adding 15ml of a cyclohexane solution of tetraethyl orthosilicate with the volume percentage concentration of 20% to the upper layer of the hexadecyl trimethyl ammonium bromide aqueous solution in the single-neck original-bottom flask, keeping the oil bath temperature at 70 ℃, and stirring for reaction for 11 hours; cetyl trimethyl ammonium bromide is used as a surfactant, and tetraethyl orthosilicate can be hydrolyzed and assembled into monodisperse virus-like mesoporous silica particles in a weak alkaline environment by triethanolamine.
And 3, after the reaction is finished, taking the aqueous phase for centrifugation, washing the aqueous phase and the ethanol for three times respectively, dispersing the aqueous phase and the ethanol into 50ml of ethanol solution containing 60 mass percent ammonium nitrate, carrying out reflux extraction on the surfactant cetyl trimethyl ammonium bromide at the oil bath temperature of 58 ℃, repeatedly extracting for 3 times, and extracting for 12 hours each time to obtain the monodisperse virus silicon oxide nanoparticles.
Step 4, ultrasonically dispersing 100 mg of monodisperse virus silicon oxide nano particles into 50ml of deionized water, and then adding 0.123g of Cu (NO)3)2•3H2And O, stirring in an oil bath at 90 ℃ for 30min, and controlling the rotation speed at 600 rpm.
Step 5, after stirring, adding 0.09g of hexamethylenetetramine into the solution obtained in the step 4, continuously stirring for reacting for 115min, after the reaction is finished, centrifugally separating and collecting a product, and washing the product with water and ethanol for three times respectively; in aqueous solution, hexamethylenetetramine is used as a reducing agent, and the rough surface of the monodisperse virus silicon oxide nano particles is beneficial to the adhesion and hydrolysis nucleation of a copper nitrate precursor, so that the appearance of the virus-like mesoporous silicon oxide can be copied, and a rough surface structure similar to virus spike protein is formed.
And 6, etching and removing the silicon oxide template in an alkaline solution, dispersing the product into a 0.1M NaOH aqueous solution, etching and removing the silicon oxide template, placing the product in a 60 ℃ oven for 24 hours, and washing ethanol with water for three times respectively to obtain the final product viroid hollow mesoporous copper oxide nano particle.
Example 3:
a method for preparing virus-like hollow mesoporous copper oxide nanoparticles comprises the following steps:
step 1, adding 3g of hexadecyl trimethyl ammonium bromide and 0.55g of triethanolamine into a 100 ml single-neck round-bottom flask, then adding 70ml of water, controlling the temperature of an oil bath to be 59 ℃, and stirring for 70min gently.
And 2, after stirring, dropwise adding 25ml of a cyclohexane solution of tetraethyl orthosilicate with the volume percentage concentration of 20% to the upper layer of the hexadecyl trimethyl ammonium bromide aqueous solution in the single-mouth original-bottom flask, keeping the oil bath temperature at 65 ℃, stirring and reacting for 13h, wherein the hexadecyl trimethyl ammonium bromide is used as a surfactant, triethanolamine is in a weakly alkaline environment, and tetraethyl orthosilicate can be hydrolyzed and assembled into monodisperse viroid-like mesoporous silica particles.
And 3, after the reaction is finished, taking the aqueous phase for centrifugation, washing the aqueous phase and the ethanol for three times respectively, dispersing the aqueous phase and the ethanol into 50ml of ethanol solution containing 60 mass percent ammonium nitrate, carrying out reflux extraction on the surfactant cetyl trimethyl ammonium bromide at the oil bath temperature of 65 ℃, repeatedly extracting for 3 times, and extracting for 12 hours each time to obtain the monodisperse virus silicon oxide nanoparticles.
Step 4, ultrasonically dispersing 100 mg of monodisperse virus silicon oxide nano particles into 50ml of deionized water, and then adding 0.123g of Cu (NO)3)2•3H2And O, stirring in an oil bath at 90 ℃ for 45min, and controlling the rotation speed at 600 rpm.
And 5, after stirring, adding 0.09g of hexamethylenetetramine into the solution obtained in the step 4, continuously stirring for reacting for 110min, after the reaction is finished, centrifugally separating and collecting a product, washing the product with water and ethanol for three times respectively in an aqueous solution, and taking the hexamethylenetetramine as a reducing agent, wherein the rough surface of the monodisperse virus silicon oxide nano particles is favorable for the adhesion and hydrolytic nucleation of a copper nitrate precursor, so that the appearance of the virus-like mesoporous silicon oxide can be copied, and a rough surface structure similar to virus spike protein is formed.
And 6, etching and removing the silicon oxide template in an alkaline solution, dispersing the product into a 0.1M NaOH aqueous solution, etching and removing the silicon oxide template, placing the product in a 60 ℃ oven for 24 hours, and washing ethanol with water for three times respectively to obtain the final product viroid hollow mesoporous copper oxide nano particle.
The preparation process of virus-like hollow mesoporous copper oxide nanometer particle includes the following steps:
the viroid-like mesoporous silica nano particles coated with copper oxide are used as a template, in a cyclohexane-water two-phase reaction system, an epitaxial single micelle growth mode is adopted, cetyl trimethyl ammonium bromide is used as a surfactant, tetraethyl orthosilicate is subjected to mild stirring in a weak alkaline environment under triethanolamine condition to be hydrolyzed and assembled into monodisperse viroid mesoporous silica particles, then the particles are used as the template, hexamethylenetetramine is used as a reducing agent, and the rough surface of the monodisperse viroid mesoporous silica nano particles is favorable for the adhesion and hydrolytic nucleation of a copper nitrate precursor, so that the morphology of the viroid mesoporous silica can be replicated, a rough surface structure similar to a viral spike protein is formed, and finally the silicon oxide template is etched and removed in an alkaline solution to obtain the viroid hollow mesoporous silica nano particles.
While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (3)

1. The method for preparing the viroid hollow mesoporous copper oxide nanoparticles is characterized by comprising the following steps of:
step 1, adding 1-5 g of hexadecyl trimethyl ammonium bromide and 0.18-0.8 g of triethanolamine into a 100 ml single-neck round-bottom flask, then adding 50-70 ml of water, controlling the temperature of an oil bath at 50-70 ℃, and stirring for 55-70 min in a mild way;
step 2, after stirring, dropwise adding 15-25 ml of cyclohexane solution to the upper layer of hexadecyl trimethyl ammonium bromide aqueous solution in a single-mouth original bottom flask, wherein the cyclohexane solution contains 20 volume percent tetraethyl orthosilicate, keeping the oil bath temperature at 50-70 ℃, and stirring for 11-13 h;
step 3, after the reaction is finished, taking the aqueous phase for centrifugation, washing the aqueous phase and ethanol for three times respectively, dispersing the aqueous phase and the ethanol into 50ml of ethanol solution, carrying out reflux extraction on the surfactant cetyl trimethyl ammonium bromide at the oil bath temperature of 55-65 ℃, and repeatedly extracting for 3 times, wherein each time lasts for 12 hours;
step 4, ultrasonically dispersing 100 mg of monodisperse virus silicon oxide nano particles into 50ml of deionized water, and then adding 0.123g of Cu (NO)3)2•3H2O, stirring in an oil bath at the temperature of 85-95 ℃ for 30-45 min, and controlling the rotating speed at 550-650 rpm;
step 5, after stirring, adding 0.09g of hexamethylenetetramine into the solution obtained in the step 4, continuously stirring and reacting for 110-120 min, after the reaction is finished, centrifugally separating and collecting a product, and washing with water and ethanol for three times respectively;
and 6, etching in an alkaline solution to remove the silicon oxide template.
2. The method for preparing viroid hollow mesoporous copper oxide nanoparticles according to claim 1, wherein the ethanol solution in step 3 contains 60% by mass of ammonium nitrate.
3. The method for producing virus-like hollow mesoporous copper oxide nanoparticles according to claim 1, wherein the step 6 of removing the silica template comprises the steps of: dispersing the product into 0.1M NaOH aqueous solution, etching to remove the silicon oxide template, placing in a 60 ℃ oven for 24 hours, washing with ethanol for three times respectively to obtain the final product viroid hollow mesoporous copper oxide nanoparticles.
CN202110758967.6A 2021-07-05 2021-07-05 Method for preparing virus-like hollow mesoporous copper oxide nanoparticles Pending CN113461045A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
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CN116003132A (en) * 2022-12-29 2023-04-25 上海轩邑新能源发展有限公司 Monodisperse porous silica-carbon sphere material, method and battery anode material

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Publication number Priority date Publication date Assignee Title
CN116003132A (en) * 2022-12-29 2023-04-25 上海轩邑新能源发展有限公司 Monodisperse porous silica-carbon sphere material, method and battery anode material
CN116003132B (en) * 2022-12-29 2023-10-27 上海轩邑新能源发展有限公司 Monodisperse porous silica-carbon sphere material, method and battery anode material

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