CN111872377B - Hollow composite material and super-assembly method thereof - Google Patents
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Abstract
The invention belongs to the field of composite materials, and particularly relates to a hollow composite material and a super-assembly method thereof. The hollow composite material core is composed of metal nano particles, and the shell is composed of silicon dioxide. Therefore, the hollow composite material and the super-assembly method thereof provided by the invention have the characteristics of simple and convenient operation, simple reaction conditions, convenient regulation and control and the like, and the obtained hollow composite material has high specific surface area, good biocompatibility and high drug molecule load.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a hollow composite material and a super-assembly method thereof.
Background
As is well known, the hollow-structure nanomaterial has the characteristics of large internal space, low density, high specific surface area and the like, and the characteristics make the hollow-structure nanomaterial widely applied to the aspects of cancer treatment, drug storage and controlled release, cosmetic production, reaction catalysis, energy storage, degradation of pigments and pollutants and the like. In the existing hollow-structure nano materials, single-component hollow-structure nano particles comprise silicon dioxide, polymers, organic molecules, metal oxides and carbonaceous materials. The multi-component hollow structure nano material can remarkably improve the performance, and particularly, the close coupling of different components and functions on the nano scale also greatly improves the overall performance, and even creates new synergistic performance.
In recent years, the preparation of high-quality and monodisperse hollow materials with different components draws wide attention, and the asymmetric multi-component hollow nano composite material with high specific surface area, good biocompatibility and high loading capacity for drug molecules becomes a hot spot of research in the field of biological medicine.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a hollow composite material and a method of super-assembling the same.
The invention provides a hollow composite material, which is characterized by comprising the following components: the core is spherical, the shell consists of a wrapping part and a tail part, the wrapping part wraps the outer surface of the core, and the tail part is hollow and provided with an opening.
In the hollow composite material provided by the invention, the hollow composite material can also have the following characteristics: wherein the diameter of the shell is 5nm-80nm, and the length of the tail part is 1nm-500 nm.
The invention also provides a super-assembly method of the hollow composite material, which is characterized by comprising the following steps: step 1, washing metal nano particles with stable citric acid, and dispersing the metal nano particles in water to obtain a metal nano particle dispersion liquid; step 2, dropwise adding the metal nanoparticle dispersion liquid into an alcohol aqueous solution, and adding mercaptocarboxylic acid and polyacrylic acid to react for a period of time under the stirring condition; and 3, after the reaction in the step 2 is finished, sequentially adding a surfactant, a silicon source and ammonia water, and slowly growing silicon dioxide on the metal nanoparticles to obtain the hollow composite material, wherein in the step 2, the volume ratio of the mercaptocarboxylic acid to the polyacrylic acid is 1: 1, the concentration of the mercapto-carboxylic acid is 5mM-25mM, in the step 3, the concentration of the surfactant is 0.0001g/ml-10g/ml, and the volume ratio of the surfactant, the silicon source and the ammonia water is 600: 1: and 90, slowly growing silicon dioxide on the metal nano particles for 4-24 hours, and preparing the hollow composite material by the super-assembly method.
The super-assembly method of the hollow composite material provided by the invention can also have the following characteristics: wherein the tail part has a length of 100nm to 500 nm.
The super-assembly method of the hollow composite material provided by the invention can also have the following characteristics: wherein the metal nanoparticles are gold nanoparticles.
The super-assembly method of the hollow composite material provided by the invention can also have the following characteristics: wherein the size of the gold nanoparticles is 10nm-500 nm.
The super-assembly method of the hollow composite material provided by the invention can also have the following characteristics: wherein, the mercapto carboxylic acid is any one of 3-mercaptopropionic acid, 4-mercaptobenzoic acid, hexadecanemercapto hexadecanoic acid or 4-mercaptophenylacetic acid, and the molecular weight of the polyacrylic acid is 1000-15000.
The super-assembly method of the hollow composite material provided by the invention can also have the following characteristics: wherein the surfactant is any one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, polyvinylpyrrolidone, Cetyl Trimethyl Ammonium Bromide (CTAB) or Cetyl Trimethyl Ammonium Chloride (CTAC).
The super-assembly method of the hollow composite material provided by the invention can also have the following characteristics: wherein the silicon source is any one of tetraethoxysilane, tetramethoxysilane, tetraethoxysilane, 1, 2-bis (triethoxysilyl) -ethane or sodium silicate.
The super-assembly method of the hollow composite material provided by the invention can also have the following characteristics: wherein the alcohol is any one of methanol, ethanol or isopropanol.
Action and Effect of the invention
According to the super-assembly method of the hollow composite material, metal nano particles are washed and dispersed in water to obtain metal nano particle dispersion liquid, then the metal nano particle dispersion liquid is dripped into an alcohol water solution, mercaptocarboxylic acid and polyacrylic acid are added under the stirring condition to react for a period of time, a surfactant and a silicon source are added, and under the catalysis of ammonia water, through super-assembly, silicon dioxide slowly grows on the metal nano particles to obtain the hollow composite material with controllable diameter and tail length.
In the process of preparing the dispersion liquid, the metal nanoparticles with stable citric acid are not easy to aggregate, the mercaptocarboxylic acid and the polyacrylic acid added in the reaction process are beneficial to the deposition of the silicon dioxide on the metal nanoparticles, and the surfactant effectively changes the interface energy of the polyacrylic acid and the surface of the silicon dioxide, so that the silicon dioxide can be combined with the polyacrylic acid.
In addition, the volume ratio of the mercaptocarboxylic acid to the polyacrylic acid is 1: 1, better target products can be obtained by adopting the proportion.
In addition, the volume ratio of the surfactant, the silicon source and the ammonia water is 600: 1: 90, experiments carried out in such proportions lead to the desired products.
According to the hollow composite material obtained by the invention, the inner core is spherical metal nano particles, the shell is formed by silicon dioxide, the shell comprises a wrapping part wrapping the metal nano particles and a tail part, and the tail part is hollow and provided with an opening, so that the hollow composite material has excellent biocompatibility.
Therefore, the super-assembly method of the hollow composite material provided by the invention has the characteristics of simple and convenient operation, simple reaction conditions, convenient regulation and control and the like, and the obtained hollow composite material has high specific surface area, good biocompatibility, high drug molecule loading performance and wide application prospect.
Drawings
FIG. 1 is a transmission electron microscope photograph of the final product of example 1;
FIG. 2 is a scanning electron microscope photograph of the final product in example 1;
FIG. 3 is a diagram of elemental analysis obtained using an X-ray energy spectrometer (EDS) in example 1;
FIG. 4 is a UV-VISIBLE absorption spectrum of gold nanoparticles and a gold/silica composite obtained using a UV-VISIBLE spectrophotometer in example 1;
FIG. 5 is a transmission electron microscope photograph of the final product of examples 2-4;
FIG. 6 is a transmission electron microscope photograph of the final products of examples 5-7.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the super-assembly method of the hollow composite material of the invention is specifically described below with reference to the embodiment and the attached drawings.
The starting materials and reagents used in the examples of the present invention were all purchased from general commercial sources, unless otherwise specified.
The invention uses a seed growth method to synthesize gold nanoparticles, and the synthesis method comprises the following steps:
first, 0.5ml of a tetrachloroauric acid solution having a concentration of 10mg/ml was added to a round flask with a condenser containing 50ml of water, and after refluxing in an oil bath for 30 minutes, 0.75ml of a sodium citrate solution having a concentration of 1% by weight was added to the boiling tetrachloroauric acid solution, and the color of the resulting solution changed from red to dark gray, then to black, and then to purple. After about 10 minutes, the solution turned red, at which stage 40nm monodisperse gold nanoparticles were formed. And after refluxing for 15min, adding 50ml of water with the temperature of 100 ℃, dropwise adding 0.1ml of NaOH solution with the concentration of 6.6mg/ml, quickly adding 0.5ml of sodium citrate solution with the concentration of 1 percent by weight and 0.5ml of tetrachloroauric acid solution with the concentration of 10mg/ml, heating for 20min, and repeating the step for three times to obtain the gold nanoparticles.
< example 1>
This example details the hollow composite and its preparation.
Step 1: washing gold nanoparticles with stable citric acid, and dispersing the gold nanoparticles in water to obtain a gold nanoparticle dispersion liquid; 2.5mL of gold nanoparticles were washed with distilled water, and the supernatant was removed. The concentrated gold nanoparticles are then dispersed in a quantity of ultra-pure water for use.
Step 2: the gold nanoparticle dispersion obtained in step 1 was dropped into a mixed solution containing 1mL of isopropyl alcohol and 1mL of deionized water, and then 25 μ L of 4-mercaptobenzoic acid having a concentration of 10mM and 25 μ L of polyacrylic acid having a molecular weight of 0.5M of 3500 were added at a stirring speed of 1000rpm/min and stirred at a stirring speed of 400rpm/min for 30 min.
And step 3: and 2, after the reaction in the step 2 is finished, sequentially adding 100 mu L of hexadecyl trimethyl ammonium bromide with the concentration of 0.15g/ml as a surfactant, 2 mu L of tetraethyl orthosilicate and 100 mu L of ammonia water, and slowly growing silicon dioxide on the gold nanoparticles under the stirring condition. The final product obtained after 24h of reaction is a hollow composite material (hereinafter referred to as composite material).
FIG. 1, panel a, is a transmission electron microscope photograph of the composite material obtained in the present example; FIG. 1, panel b, is an enlarged view of a single TEM of the composite obtained in the present example; FIG. 2 is a scanning electron microscope photograph of the composite material obtained in this example.
As shown in fig. 1-2, the composite material obtained in this embodiment is integrally tadpole-shaped, the composite material shell wrapping portion is the tadpole head, the composite material tail portion is the tadpole tail, the hollow diameter of the tail portion is 55nm, and the length of the tail portion is 210 nm.
The composite material was subjected to elemental analysis using an X-ray energy spectrometer (EDS) with an instrument model of Tecnai G2F 20S-Twin, and the results of the detection are shown in FIG. 3.
FIG. 3 is an elemental analysis chart obtained by using an X-ray energy spectrometer (EDS) in example 1. Wherein, the topographic map obtained by analyzing the distribution state of all elements in the composite material is shown in figure 3 a; the morphology obtained by analyzing the distribution state of the oxygen element in the composite material is shown in figure 3 b; the topographic map obtained by analyzing the distribution state of the silicon element in the composite material is shown in figure 3 c; the distribution state of the gold element in the composite material is analyzed to obtain a topographic map shown in fig. 3 d.
As can be seen from a-d in fig. 3, the composite material is integrally in a tadpole shape, the head of each tadpole is an inner core wrapped by an outer shell, the inner core is spherical gold nanoparticles, and the tail of each tadpole is a hollow part of the outer shell. The oxygen element and the silicon element in the composite material are uniformly distributed in the shell of the composite material, the formed silicon dioxide shell is in a pocket shape, one end of the silicon dioxide shell is closed, and the other end of the silicon dioxide shell is open.
The silicon dioxide has no absorption peak in the ultraviolet visible light absorption spectrum, and as can be seen from the ultraviolet visible light absorption spectrum in fig. 4, the maximum absorption peak of the silicon dioxide before and after growing is 550nm, which is the absorption peak of gold. As can be seen from fig. 3, silica grows on the gold nanoparticles, and the generated shell wraps the gold nanoparticles.
< example 2>
The hollow composite material of this example was prepared in the same manner as in example 1 except that the concentration of 4-mercaptobenzoic acid was changed to 5mM, and the final product was a hollow composite material having a hollow diameter of the tail portion of 80nm and a length of the tail portion of 125 nm.
< example 3>
The hollow composite material of this example was prepared in the same manner as in example 1 except that the concentration of 4-mercaptobenzoic acid was changed to 20mM, and the final product was a hollow composite material having a hollow diameter of the tail portion of 5nm and a length of the tail portion of 500 nm.
< example 4>
The hollow composite material of this example was prepared in the same manner as in example 1 except that the concentration of 4-mercaptobenzoic acid was changed to 30mM, and the final product was a hollow composite material in which the tail portion was changed to be solid and the length of the tail portion was 250 nm.
FIG. 5 is a Transmission Electron Micrograph (TEM) of the final product of examples 2-4.
FIG. 5, panel a, FIG. 5, is a TEM image of the product obtained in example 2, panel b, FIG. 5, is a TEM image of the product obtained in example 3, and panel c, FIG. 5, is a TEM image of the product obtained in example 4.
As shown in FIG. 5, 5mM of 4-mercaptobenzoic acid was added in example 2, and the resulting composite material had a hollow diameter of 80nm and a tail length of 125 nm; in example 3, 20mM of 4-mercaptobenzoic acid was added to obtain a composite material having a hollow diameter of 5nm and a tail length of 500 nm; in example 4, 30mM of 4-mercaptobenzoic acid was added, and the resulting composite had a solid tail portion with a tail length of 250 nm.
< example 5>
This example details the hollow composite and its preparation.
Step 1: washing gold nanoparticles with stable citric acid, and dispersing the gold nanoparticles in water to obtain a gold nanoparticle dispersion liquid; 2.5mL of gold nanoparticles were washed with distilled water, and the supernatant was removed. The concentrated gold nanoparticles are then dispersed in a quantity of ultra-pure water for use.
Step 2: the gold nanoparticle dispersion obtained in step 1 was dropped into a mixed solution containing 1mL of isopropyl alcohol and 1mL of deionized water, and then 25 μ L of 4-mercaptobenzoic acid having a concentration of 10mM and 25 μ L of polyacrylic acid having a molecular weight of 0.5M of 3500 were added at a stirring speed of 1000rpm/min and stirred at a stirring speed of 400rpm/min for 30 min.
And step 3: and 2, after the reaction is finished, sequentially adding 100 mu L of hexadecyl trimethyl ammonium bromide with the concentration of 0.15g/ml serving as a surfactant, 2 mu L of tetraethyl orthosilicate and 100 mu L of ammonia water, slowly growing silicon dioxide on the gold nanoparticles under the stirring condition, and reacting for 24 hours to obtain a final product, namely the hollow composite material, wherein the hollow diameter of the tail part of the composite material is 55nm, and the length of the tail part of the composite material is 210 nm.
< example 6>
In this example, the preparation method of the hollow composite material is the same as that in example 5, only the reaction time in step 3 is changed to 2 hours, and the obtained final product does not grow a tail part, and only the silica shell wraps the gold nanoparticles.
< example 7>
The preparation method of the hollow composite material in the embodiment is the same as that of the embodiment 5, and the final product is the hollow composite material by changing the reaction time in the step 3 to 4h, wherein the hollow diameter of the tail part of the composite material is 55nm, and the length of the tail part is 100 nm.
FIG. 6 is a Transmission Electron Micrograph (TEM) of the final product of examples 5-7.
FIG. 6, panel a, FIG. 6, is a TEM image of the product obtained in example 6, panel b, FIG. 6, is a TEM image of the product obtained in example 7, and panel c, FIG. 6, is a TEM image of the product obtained in example 5.
As shown in fig. 6, the growth time of the silica in example 6 was 2 hours, the obtained composite failed to grow the tail portion, the growth time of the silica in example 7 was 4 hours, the length of the tail portion of the obtained composite was 100nm, the hollow diameter was 55nm, the growth time of the silica in example 5 was 24 hours, the length of the tail portion of the obtained composite was 210nm, and the hollow diameter was 55 nm.
Effects and effects of the embodiments
According to the hollow composite material related by the embodiment, washed citric acid-stable gold nanoparticles are dispersed in water, then the obtained gold nanoparticle dispersion liquid is dropwise added into an alcohol aqueous solution, mercaptocarboxylic acid and polyacrylic acid are added under the stirring condition to serve as a mixture, a surfactant is added after reaction, a silicon source is added, and under the catalysis of ammonia water, silica slowly grows on the gold nanoparticles through super-assembly, so that the hollow composite material is obtained.
In the process of preparing the dispersion, the gold nanoparticles with stable citric acid are not easy to aggregate, the mercaptocarboxylic acid and the polyacrylic acid added in the reaction process are beneficial to the deposition of the silicon dioxide on the gold nanoparticles, and the surfactant effectively changes the interface energy of the polyacrylic acid and the surface of the silicon dioxide, so that the silicon dioxide can be combined with the polyacrylic acid.
In addition, the volume ratio of mercaptocarboxylic acid to polyacrylic acid is 1: 1, can reach comparatively ideal experimental effect.
In addition, the volume ratio of the surfactant, the silicon source and the ammonia water is 600: 1: 90, the target effect can be achieved by adopting the proportion.
The hollow composite material obtained in the embodiment has higher uniform particle size and monodispersity, so that the application value is very high, different hollow diameters can better load molecular drugs with different sizes, and the tail part of the hollow opening serving as a micro-nano reactor can be communicated with the external environment.
In addition, as can be seen from examples 1 to 4, the concentration of 4-mercaptobenzoic acid was 5mM to 25mM, the hollow diameter of the hollow composite material was 5nm to 80nm, and the hollow diameter of the hollow composite material could be changed as the concentration of 4-mercaptobenzoic acid was varied. As can be seen from example 5, the concentration of 4-mercaptobenzoic acid was 30mM and the tail portion of the composite material was completely solid. From the results of examples 1 to 5, it is understood that the tail structure of the composite material can be controlled to be hollow or solid by changing the concentration of 4-mercaptobenzoic acid.
As can be seen from examples 6 and 8, the growth time of silica on the gold nanoparticles is 4h to 24h, the tail length of the hollow composite material is 100nm to 210nm, and the tail portion of the hollow composite material grows as the growth time of silica on the gold nanoparticles increases. As can be seen from example 7, the growth time of silica on the gold nanoparticles was 2h, and no tail portion was grown from the hollow composite. From the results of examples 6 to 8, it can be seen that the length of the tail of the hollow composite material can be controlled by changing the growth time of the silica on the gold nanoparticles, thereby achieving the desired effect.
Therefore, the super-assembly method of the hollow composite material provided by the embodiment has the characteristics of simplicity and convenience in operation, simple reaction conditions, easiness in industrialization and the like, and the obtained hollow composite material has the advantages of high specific surface area, good biocompatibility, high drug molecule loading capacity and wide application prospect.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
Claims (8)
1. A hollow composite material, comprising:
an inner core composed of metal nanoparticles and an outer shell composed of silicon dioxide,
wherein the inner core is spherical, the outer shell consists of a wrapping part and a tail part,
the wrapping part wraps on the outer surface of the inner core, the tail part is hollow and is provided with an opening,
the hollow composite material is integrally in a tadpole shape, the wrapping part is a tadpole head, the tail part is a tadpole tail,
the hollow diameter of the tail part is 5nm-80nm,
the tail portion has a length of 100nm to 500 nm.
2. The method for super-assembling a hollow composite material according to claim 1, comprising the steps of:
step 1, washing metal nano particles with stable citric acid, and dispersing the metal nano particles in water to obtain a metal nano particle dispersion liquid;
step 2, dropwise adding the metal nanoparticle dispersion liquid into an alcohol aqueous solution, and adding mercaptocarboxylic acid and polyacrylic acid to react for a period of time under the stirring condition;
step 3, after the reaction in step 2 is finished, sequentially adding a surfactant, a silicon source and ammonia water, slowly growing silicon dioxide on the metal nano-particles to obtain a hollow composite material,
in step 2, the volume ratio of the mercaptocarboxylic acid to the polyacrylic acid is 1: 1, the concentration of the mercapto carboxylic acid is 5mM-25mM,
in the step 3, the concentration of the surfactant is 0.0001g/ml-10g/ml, and the volume ratio of the surfactant to the silicon source to the ammonia water is 600: 1: 90,
the silicon dioxide slowly grows on the metal nanoparticles for 4-24 hours.
3. The method of super-assembling a hollow composite material according to claim 2, wherein:
wherein the metal nanoparticles are gold nanoparticles.
4. A method of super-assembling a hollow composite material according to claim 3, wherein:
wherein the size of the gold nanoparticles is 10nm-500 nm.
5. The method of super-assembling a hollow composite material according to claim 2, wherein:
wherein the mercapto carboxylic acid is any one of 3-mercaptopropionic acid, 4-mercaptobenzoic acid, hexadecanemercapto hexadecanoic acid or 4-mercaptophenylacetic acid,
the molecular weight of the polyacrylic acid is 1000-15000.
6. The method of super-assembling a hollow composite material according to claim 2, wherein:
wherein the surfactant is any one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, polyvinylpyrrolidone, Cetyl Trimethyl Ammonium Bromide (CTAB) or Cetyl Trimethyl Ammonium Chloride (CTAC).
7. The method of super-assembling a hollow composite material according to claim 2, wherein:
wherein the silicon source is any one of tetraethoxysilane, tetramethoxysilane, tetraethoxysilane, 1, 2-bis (triethoxysilyl) -ethane or sodium silicate.
8. The method of super-assembling a hollow composite material according to claim 2, wherein:
wherein the alcohol is any one of methanol, ethanol or isopropanol.
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