CN116271092B - Shape-controllable nanoscale hollow carbon sphere drug carrier and preparation method thereof - Google Patents

Shape-controllable nanoscale hollow carbon sphere drug carrier and preparation method thereof Download PDF

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CN116271092B
CN116271092B CN202310192187.9A CN202310192187A CN116271092B CN 116271092 B CN116271092 B CN 116271092B CN 202310192187 A CN202310192187 A CN 202310192187A CN 116271092 B CN116271092 B CN 116271092B
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silicon dioxide
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CN116271092A (en
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魏强
高静
于海洋
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Sichuan University
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/50—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates
    • A61K47/69—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the conjugate being characterised by physical or galenical forms, e.g. emulsion, particle, inclusion complex, stent or kit
    • A61K47/6921—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the conjugate being characterised by physical or galenical forms, e.g. emulsion, particle, inclusion complex, stent or kit the form being a particulate, a powder, an adsorbate, a bead or a sphere
    • A61K47/6923—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the conjugate being characterised by physical or galenical forms, e.g. emulsion, particle, inclusion complex, stent or kit the form being a particulate, a powder, an adsorbate, a bead or a sphere the form being an inorganic particle, e.g. ceramic particles, silica particles, ferrite or synsorb
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/50—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates
    • A61K47/51—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent
    • A61K47/56—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent the modifying agent being an organic macromolecular compound, e.g. an oligomeric, polymeric or dendrimeric molecule
    • A61K47/59—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent the modifying agent being an organic macromolecular compound, e.g. an oligomeric, polymeric or dendrimeric molecule obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyureas or polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a morphology-controllable nanoscale hollow carbon sphere drug carrier and a preparation method thereof. The invention provides a novel preparation method of a shape-controllable nanoscale hollow carbon sphere, which utilizes oxidation-self polymerization of dopamine to form a polydopamine layer on the surface of synthesized nanoscale spherical silicon dioxide, and prepares the nanoscale hollow carbon sphere by subsequent heat treatment and etching away of inner core silicon dioxide. The preparation method has the advantages of simple steps, low cost, good repeated stability, high purity of the obtained hollow carbon spheres, uniform particle size and few defects, can meet the basic requirement of the hollow carbon spheres as drug carriers, and can be used for large-scale preparation at the laboratory level.

Description

Shape-controllable nanoscale hollow carbon sphere drug carrier and preparation method thereof
Technical Field
The invention relates to the technical field of nano material preparation, in particular to a hollow nano carbon sphere, and relates to a morphology-controllable nanoscale hollow carbon sphere drug carrier and a preparation method thereof.
Background
The carbon nanomaterial has the advantages of good biocompatibility, hydrophilicity, permeability and the like, and can be widely applied to the field of biological medicine as a medicine carrier. The carbon nanomaterial used for drug delivery at present mainly comprises one-dimensional tubular carbon nanotubes and two-dimensional layered graphene. However, there is still a difficulty in precisely controlling the microstructure of the carbon nanotubes or graphene, such as the ratio of the diameter to the length of the carbon nanotubes and the number of layers and the spacing of the graphene. In contrast, the three-dimensional nano hollow carbon spheres have higher porosity, larger specific surface area and morphology structure which is easier to control accurately. The main flow method for preparing the nano hollow carbon spheres is a template method, and the selected template is a silicon dioxide-sodium tripolyphosphate-chitosan system: such as Chinese patent: a preparation method of a porous hollow carbon nanosphere, which has the following patent application number: 202210683075.9; melamine-iron-organic polymer system: such as Chinese patent: a preparation method of porous graphitized hollow carbon microspheres, which has the following patent application number: 201911273266.2; nickel nitrate-trimesic acid-polyvinylpyrrolidone system: such as Chinese patent: a method for preparing a porous hollow carbon material by etching, which comprises the following steps of: 20201201674. X; p123 sodium oleate-glucose system: such as Chinese patent: a hollow spherical boron carbon nitrogen material and a preparation method thereof, patent application number: 202210807667.7; polytetrafluoroethylene-ferrocene-ferric trichloride system: such as Chinese patent: a hollow carbon sphere, a preparation method and application thereof, and the patent application number is: 202110325859.X; silica-polyaniline-polypyrrole system: such as Chinese patent: a method for preparing hollow carbon microspheres rapidly and efficiently, which has the following patent application number: 202210853920.2.
in summary, the template system currently used for preparing the drug-loaded carrier of the hollow carbon nanospheres often needs the mutual combination of three different chemical substances, and in addition, the addition of an inducer, a cross-linking agent or a catalyst and the like leads to the rapid increase of the preparation cost, and the appearance of the hollow carbon nanospheres also has larger defects (collapse, different particle size and size) and residual multiple harmful elements which are unfavorable to cells and the like.
Therefore, the nano hollow carbon sphere drug carrier with less synthesis defects and higher purity is particularly important for the field of biological medicine by controlling the preparation cost.
Disclosure of Invention
The invention aims to solve the following problems of the existing hollow carbon spheres: 1. the carbon spheres have larger defects; 2. the particle size of the particles is not uniform; 3. the purity is not high, and a large amount of other impurity elements are contained. The preparation method of the morphology-controllable nanoscale hollow carbon sphere drug-loaded carrier can be realized at the laboratory level. The method has the advantages of low preparation cost, good repeated stability, high purity of the prepared hollow carbon spheres, uniform particle size distribution and good sphericity.
The invention provides a technical scheme that: a preparation method of a morphology-controllable nanoscale hollow carbon sphere drug-loaded carrier, which comprises the following steps:
s1, providing nanoscale spherical silicon dioxide;
s2, forming a compact polydopamine layer on the surface of the spherical silicon dioxide;
s3, carrying out heat treatment on the polydopamine layer to obtain a silica-coated nano carbon sphere;
and S4, etching the silica-coated nano carbon spheres to obtain hollow nano carbon spheres.
Preferably, in step S1, the specific preparation method is as follows: weighing 1-4ml of 25% ammonia water, 12-48ml of 99.5% absolute ethyl alcohol and 80-100ml of deionized water, vigorously stirring for 20-40min, dropwise adding 1-3ml tetraethoxysilane, and continuously vigorously stirring for 15-45min.
Preferably, in step S2, the specific preparation method is as follows: adding 50mg/ml dopamine hydrochloride 6-12ml into the spherical nano silicon dioxide solution prepared in the step S1 for self-polymerization for 12-36 hours to obtain brown mixed solution, washing with deionized water to be neutral, and carrying out suction filtration to obtain a brown black solid, namely the spherical nano silicon dioxide coated with polydopamine.
Preferably, in step S3, the conductive nanocarbon balls are obtained by high temperature-cracking under an inert gas atmosphere, wherein the inert gas may be selected from nitrogen, argon, and helium; the preparation method comprises the following steps: drying the spherical nano silicon dioxide coated with polydopamine obtained in the step S2 in an oven at 80 ℃ for 12 hours, carbonizing the spherical nano silicon dioxide by using a tube furnace with temperature programming under the protection of nitrogen atmosphere, wherein the temperature raising rate is 5-10 ℃/min, the temperature raising is 700-900 ℃, the heat preservation time is 120-240min, and finally grinding to obtain the nano carbon sphere coated with silicon dioxide.
Preferably, in step S4, the specific preparation method is as follows: washing the nano carbon spheres coated with the silicon dioxide obtained in the step S3 in 10wt% hydrofluoric acid solution for 30-60min to etch away the inner core silicon dioxide, washing with deionized water until neutral suction filtration is carried out to obtain black solid, and drying to obtain the nano hollow carbon spheres.
The beneficial effects of the invention are as follows:
the provided nano hollow carbon sphere has novel design thought, poly-dopamine (PDA) has the property similar to mussels and barnacle adhesion proteins, can be adhered to the surfaces of almost all materials, forms a PDA layer on the surfaces of synthetic silicon dioxide by oxidation-self polymerization of dopamine, and is prepared through subsequent treatment. The preparation method has the advantages of simple steps, low cost, good repeated stability, high purity of the obtained hollow carbon spheres, uniform particle size and few defects, and can meet the requirement of large-scale preparation on the laboratory level.
Drawings
FIG. 1 is a scanning electron microscope image of a nanoscale hollow carbon sphere of example 1;
FIG. 2 is a transmission electron microscope image of the hollow carbon nanospheres of example 1;
FIG. 3 is an EDS element energy spectrum of the nano-scale hollow carbon sphere of example 1;
FIG. 4 is a transmission electron microscope image of the hollow carbon nanospheres of example 2;
FIG. 5 is a transmission electron microscope image of the hollow carbon nanospheres of example 3;
fig. 6 is a transmission electron microscope image of the nano-scale hollow carbon sphere of comparative example 5.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
Example 1:
the embodiment provides a preparation method of a morphology-controllable nanoscale hollow carbon sphere drug carrier, which comprises the following steps:
s1, providing nanoscale silicon dioxide with controllable morphology;
s2, forming a compact polydopamine layer on the surface of the spherical silicon dioxide;
s3, carrying out heat treatment on the polydopamine layer to obtain a silica-coated nano carbon sphere;
and S4, etching the silica-coated nano carbon spheres to obtain hollow nano carbon spheres.
In step S1, the silica is prepared by hydrolysis-condensation of tetraethoxysilane under alkaline conditions. The preparation method comprises the following steps: 1ml of 25% ammonia water, 12ml of 99.5% absolute ethanol and 80ml of deionized water are weighed, vigorously stirred for 20min, 1ml of tetraethoxysilane is added dropwise, and vigorously stirred for 15min.
In step S2, the dense polydopamine layer needs to be formed in an alkaline environment in step S1 by oxidation-polymerization of dopamine itself. The preparation method comprises the following steps: adding 50mg/ml dopamine hydrochloride 6ml into the spherical nano silicon dioxide solution prepared in the step S1 for self-polymerization for 12 hours to obtain brown mixed solution, and then washing with deionized water to neutrality and suction filtering to obtain brown black solid, namely polydopamine coated spherical nano silicon dioxide.
In the step S3, the polydopamine coated spherical nano silica is obtained by high temperature-cracking under the atmosphere of inert gas. The preparation method comprises the following steps: and (3) drying the spherical nano silicon dioxide coated with polydopamine obtained in the step (S2) in an oven at 80 ℃ for 12 hours, carbonizing the spherical nano silicon dioxide by using a tube furnace capable of programming temperature under the protection of nitrogen atmosphere, wherein the temperature rising rate is 5 ℃/min, the temperature rising is 700 ℃, the heat preservation time is 120min, and finally grinding to obtain the nano carbon sphere coated with silicon dioxide.
In the step S4, washing the nano carbon spheres coated with the silicon dioxide obtained in the step S3 in 10wt% hydrofluoric acid solution for 30min to etch away the inner core silicon dioxide, washing with deionized water until neutral suction filtration is carried out to obtain black solid, and drying to obtain the nano hollow carbon spheres.
As shown in a scanning electron microscope in FIG. 1, the prepared nano-scale hollow carbon spheres have good sphericity, few defect sites and no large-area collapse.
As shown in a transmission electron microscope in FIG. 2, the prepared nanoscale hollow carbon sphere has good hollowness, the inner core silicon dioxide is completely removed, and the thickness of the carbon layer is uniform.
As shown in the EDS element energy spectrum of FIG. 3, the prepared nano-scale hollow carbon spheres have high purity, only consist of carbon elements, and do not contain redundant impurity elements.
Example 2:
the embodiment provides a preparation method of a morphology-controllable nanoscale hollow carbon sphere drug carrier, which comprises the following steps:
s1, providing nanoscale silicon dioxide with controllable morphology;
s2, forming a compact polydopamine layer on the surface of the spherical silicon dioxide;
s3, carrying out heat treatment on the polydopamine layer to obtain a silica-coated nano carbon sphere;
and S4, etching the silica-coated nano carbon spheres to obtain hollow nano carbon spheres.
In step S1, the silica is prepared by hydrolysis-condensation of tetraethoxysilane under alkaline conditions. The preparation method comprises the following steps: 2ml of 25% ammonia water, 36ml of 99.5% absolute ethanol and 90ml of deionized water are measured, the mixture is vigorously stirred for 30min, 2ml of tetraethoxysilane is added dropwise, and the vigorous stirring is continued for 30min.
In step S2, the dense polydopamine layer needs to be formed in an alkaline environment in step S1 by oxidation-polymerization of dopamine itself. The preparation method comprises the following steps: adding 50mg/ml dopamine hydrochloride 10ml into the spherical nano silicon dioxide solution prepared in the step S1 for self-polymerization for 24 hours to obtain brown mixed solution, and then washing with deionized water to neutrality and suction filtering to obtain brown black solid, namely polydopamine coated spherical nano silicon dioxide.
In the step S3, the polydopamine coated spherical nano silica is obtained by high temperature-cracking under the atmosphere of inert gas. The preparation method comprises the following steps: and (3) drying the spherical nano silicon dioxide coated with polydopamine obtained in the step (S2) in an oven at 80 ℃ for 12 hours, carbonizing the spherical nano silicon dioxide by using a tube furnace capable of programming temperature under the protection of nitrogen atmosphere, wherein the temperature rising rate is 8 ℃/min, the temperature rising is 800 ℃, the heat preservation time is 180min, and finally grinding to obtain the nano carbon sphere coated with silicon dioxide.
In the step S4, washing the nano carbon spheres coated with the silicon dioxide obtained in the step S3 in 10wt% hydrofluoric acid solution for 45min to etch away the inner core silicon dioxide, washing with deionized water until neutral suction filtration is carried out to obtain black solid, and drying to obtain the nano hollow carbon spheres.
As shown in a transmission electron microscope in FIG. 4, the prepared nanoscale hollow carbon sphere has good hollowness, the inner core silicon dioxide is completely removed, and the thickness of the carbon layer is uniform.
Example 3:
the embodiment provides a preparation method of a morphology-controllable nanoscale hollow carbon sphere drug carrier, which comprises the following steps:
s1, providing nanoscale silicon dioxide with controllable morphology;
s2, forming a compact polydopamine layer on the surface of the spherical silicon dioxide;
s3, carrying out heat treatment on the polydopamine layer to obtain a silica-coated nano carbon sphere;
and S4, etching the silica-coated nano carbon spheres to obtain hollow nano carbon spheres.
In step S1, the silica is prepared by hydrolysis-condensation of tetraethoxysilane under alkaline conditions. The preparation method comprises the following steps: weighing 4ml of 25% ammonia water, 48ml of 99.5% absolute ethyl alcohol and 100ml of deionized water, vigorously stirring for 40min, dropwise adding 3ml of tetraethoxysilane, and continuously vigorously stirring for 45min.
In step S2, the dense polydopamine layer needs to be formed in an alkaline environment in step S1 by oxidation-polymerization of dopamine itself. The preparation method comprises the following steps: adding 12ml of dopamine hydrochloride with the concentration of 50mg/ml into the spherical nano silicon dioxide solution prepared in the step S1 for self-polymerization for 36 hours to obtain brown mixed solution, and then washing with deionized water to neutrality and suction filtering to obtain brown black solid, namely the spherical nano silicon dioxide coated with polydopamine.
In the step S3, the polydopamine coated spherical nano silica is obtained by high temperature-cracking under the atmosphere of inert gas. The preparation method comprises the following steps: and (3) drying the spherical nano silicon dioxide coated with polydopamine obtained in the step (S2) in an oven at 80 ℃ for 12 hours, carbonizing the spherical nano silicon dioxide by using a tube furnace capable of programming temperature under the protection of nitrogen atmosphere, wherein the temperature rising rate is 10 ℃/min, the temperature rising is 900 ℃, the heat preservation time is 240min, and finally grinding to obtain the nano carbon sphere coated with silicon dioxide.
In the step S4, washing the nano carbon spheres coated with the silicon dioxide obtained in the step S3 in 10wt% hydrofluoric acid solution for 60min to etch away the inner core silicon dioxide, washing with deionized water until neutral suction filtration is carried out to obtain black solid, and drying to obtain the nano hollow carbon spheres.
As shown in a transmission electron microscope in FIG. 5, the prepared nanoscale hollow carbon sphere has good hollowness, the inner core silicon dioxide is completely removed, and the thickness of the carbon layer is uniform.
Comparative example 1:
in the preparation method of patent 202210683075.9, the raw materials used are a ternary system of silicon dioxide, sodium tripolyphosphate and chitosan, the reaction temperature is 80 ℃, the reaction pressure is normal pressure, and the patent does not provide microscopic dimensions for preparing the carbon spheres. Comparative example 2:
in the preparation method of the patent 201911273266.2, the raw materials used are ternary system of melamine, iron and organic polymer, the reaction temperature is 40 ℃, the reaction pressure is normal pressure, and the size of the prepared carbon spheres is in a micron order.
Comparative example 3:
in the preparation method of the patent 20201201674. X, the raw materials used are ternary system of nickel nitrate, trimesic acid and polyvinylpyrrolidone, the reaction temperature is 130-170 ℃, the reaction pressure is normal pressure, and the size of the prepared carbon spheres is nano-scale.
Comparative example 4:
in the preparation method of the patent 202210807667.7, the raw materials used are ternary system of P123, sodium oleate and glucose, the reaction temperature is 165-195 ℃, the reaction pressure is high pressure, and the size of the prepared carbon sphere is nano-scale.
Comparative example 5:
in the preparation method of patent 202110325859.X, the raw materials used are ternary system of silicon dioxide, polyaniline and polypyrrole, the reaction temperature is 400 ℃, the reaction pressure is high pressure, and the size of the prepared carbon sphere is nano-scale.
As shown in a transmission electron microscope image in FIG. 6, the prepared hollow nano carbon spheres have nonuniform particle size and poor sphericity. In contrast, the hollow nano carbon spheres prepared by the method are good in spherical integrity, full in granularity, uniform in particle size and high in purity.
In summary, table 1 shows that the prior related invention patent is compared with the technical statistics of the patent of the present application in terms of the reaction raw material, the reaction temperature, the reaction pressure and the carbon sphere size, the reaction raw material of the present invention is mainly a binary system of silicon dioxide and dopamine, the reaction temperature is normal temperature, and the reaction pressure is normal pressure, which can effectively reduce the preparation cost.
Table 1:
the above-described embodiments are provided to illustrate the gist of the present invention, but are not intended to limit the scope of the present invention. It will be understood by those skilled in the art that various modifications and equivalent substitutions may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.

Claims (2)

1. A preparation method of a morphology-controllable nanoscale hollow carbon sphere drug-carrying carrier is characterized by comprising the following steps of: the method comprises the following steps:
s1, providing nanoscale spherical silicon dioxide;
s2, forming a compact polydopamine layer on the surface of the spherical silicon dioxide;
s3, carrying out heat treatment on the polydopamine layer to obtain a silica-coated nano carbon sphere;
s4, etching the silica coated nano carbon spheres to obtain hollow nano carbon spheres;
step S2, adding 6-12ml of dopamine hydrochloride with the concentration of 50mg/ml into the spherical nano silicon dioxide solution prepared in the step S1 for self-polymerization for 12-36 hours to obtain brown mixed solution, washing with deionized water to be neutral, and carrying out suction filtration to obtain a brown black solid, namely the spherical nano silicon dioxide coated with polydopamine;
step S3, drying the spherical nano silicon dioxide coated with polydopamine obtained in the step S2 in an oven at 80 ℃ for 12 hours, carbonizing the spherical nano silicon dioxide by using a tube furnace with temperature programming under the protection of nitrogen atmosphere, wherein the temperature raising rate is 5-10 ℃/min, the temperature raising is 700-900 ℃ and the heat preservation time is 120-240min, and finally grinding to obtain the nano carbon sphere coated with silicon dioxide;
and S4, washing the nano carbon spheres coated with the silicon dioxide obtained in the step S3 in 10wt% hydrofluoric acid solution for 30-60min to etch away the inner core silicon dioxide, washing with deionized water until neutral, performing suction filtration to obtain black solid, and drying to obtain the nano hollow carbon spheres.
2. The method of manufacturing according to claim 1, wherein: step S1 is to measure 1-4ml of 25% ammonia water, 12-48ml of 99.5% absolute ethyl alcohol and 80-100ml of deionized water, vigorously stir for 20-40min, dropwise add 1-3ml tetraethoxysilane, and continuously vigorously stir for 15-45min.
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