CN110280779B - Core-shell type nanogold composite material, and preparation method and application thereof - Google Patents
Core-shell type nanogold composite material, and preparation method and application thereof Download PDFInfo
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- 239000010931 gold Substances 0.000 claims abstract description 86
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 22
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 13
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Abstract
The invention provides a core-shell type nano-gold composite material, a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing CTAB, a chloroauric acid solution, a silver nitrate solution, an ascorbic acid solution and a sodium borohydride solution to obtain a gold nanorod solution; after the gold nanorod solution is subjected to ultrasonic treatment, a methanol solution of TEOS is dripped for reaction to prepare a mesoporous silica gold nanorod solution; adding methanol solution of APTES for carrying out an amination reaction to obtain an aminated mesoporous silica gold nanorod solution; and adding the gold nanocluster solution into the aminated mesoporous silica gold nanorod solution, and reacting to obtain the core-shell type nano-gold composite material. The material improves the photo-thermal performance of the gold nanorods, enables the gold nanorod carriers to have the fluorescence characteristic, and has good application potential in photo-thermal treatment and biological imaging. The preparation method solves the problems of poor biocompatibility and poor stability of the gold nanorods.
Description
Technical Field
The invention relates to a core-shell type nano-gold composite material, a preparation method and application thereof, belonging to the technical field of nano-materials and special materials.
Background
Gold nanorods have gained wide attention due to their unique physicochemical properties and their potential biophotonic applications, such as photothermal therapy, biosensing, molecular imaging, etc. Like spherical gold nanoparticles, gold nanorods also have specific surface plasmon resonance characteristics. By controlling their aspect ratio, longitudinal surface plasmon resonance characteristics in the range from visible light to near infrared can be obtained. In addition, the LP of the gold nanorods is adjustable in the near infrared region. When the near-infrared light source irradiates, the gold nanorods can quickly become a high-concentration local heat source due to the plasma resonance characteristic, and the generated heat is enough to kill cancer cells. Because of this property, it is widely used in photothermal therapy systems. However, the gold nanorods have high biotoxicity and poor stability, and the photothermal treatment effect after entering the body is not ideal.
Gold nanoclusters are a special type of gold nanomaterial with dimensions less than 3 nm. Unlike gold nanorods, the gold nanorods cannot show surface plasmon resonance characteristics, and an ultraviolet absorption peak is located in a visible light region, and a fluorescence emission peak can be from a visible light region to a near infrared region. The gold nanoclusters have the characteristics of long fluorescence lifetime, large Stokes shift and good biocompatibility, and are often used for biological imaging and fluorescence sensing.
The mesoporous silica has wide application range, good biocompatibility and controllable shape and size, and is a novel inorganic biomaterial with high specific surface area and large pore volume. The mesoporous silica mesoporous material has the characteristics of high chemical stability, high biocompatibility, convenient synthesis, low cost and the like, and has great application prospect in other fields such as biomedicine and genetic engineering besides the application field of the traditional mesoporous material.
Photothermal therapy is a non-invasive and local way of treating tumors. The tumor cells are ablated by generating enough heat under the irradiation of near-infrared laser mainly through a photothermal conversion agent. It has the features of less invasion, high specificity, less side effect, fast acting, etc. Due to the high power laser irradiation used in the treatment, there is inevitable damage to normal tissue in the vicinity of the tumor tissue. Therefore, the photothermal performance of the photothermal agent is improved, and enough photothermal heat can be generated to ablate tumor cells under the condition of low power. Gold nanorods are a photo-thermal material. The photo-thermal properties are general, and when high-energy laser irradiation is performed, the shape is collapsed and deformed, resulting in the reduction of the photo-thermal properties. Therefore, the improvement of the photo-thermal stability and photo-thermal performance of the gold nano-material is a major challenge in photo-thermal treatment.
Disclosure of Invention
In order to solve the defects in the prior art, the invention discloses a core-shell type nano-gold composite material, a preparation method and application thereof, the material improves the photo-thermal performance of gold nanorods, solves the problems of poor biocompatibility and poor stability of the gold nanorods, enables the gold nanorod carriers to have fluorescence characteristics, and has good application potential in photo-thermal treatment and biological imaging.
The invention is realized by the following technical scheme:
a preparation method of a core-shell type nano-gold composite material comprises the following steps:
1) preparing a gold nanorod solution by a seed-free method:
dissolving CTAB in ultrapure water, sequentially adding a chloroauric acid solution, a silver nitrate solution, an ascorbic acid solution and a sodium borohydride solution, stirring for 10-30s in a water bath at 30-40 ℃, standing for 4-8h, centrifuging, removing an upper clear liquid to obtain a lower colloidal solution, washing with deionized water, removing the redundant CTAB solution, and taking the lower colloidal solution to obtain a gold nanorod solution;
2) preparing a gold nanorod solution wrapped by mesoporous silica:
adding deionized water into the gold nanorod solution obtained in the step 1), performing ultrasonic treatment for 10-20min, adjusting the pH value of the solution to 9-10 in a water bath at 30-40 ℃, and rapidly stirring for 20-40 min;
then, dripping a methanol solution of TEOS for three times, wherein the interval is 20-40min each time; continuously reacting for 30-40h under the stirring state;
finally, centrifuging, and washing with water and alcohol respectively to prepare a mesoporous silica gold nanorod solution;
3) carrying out amination modification on the gold nanorods wrapped by the mesoporous silica:
adding the mesoporous silica gold nanorod solution obtained in the step 2) into an APTES solution. Then, adding methanol and hydrochloric acid, heating under reflux for 4-8h at 50-70 ℃, and removing the CTAB template;
centrifuging the refluxed substance, taking the lower layer precipitate to obtain aminated mesoporous silica gold nanorods;
4) preparing a gold nanocluster solution:
adding a bovine serum albumin solution into a chloroauric acid solution, stirring for 1-5min under the condition of a water bath at 30-40 ℃, then adding a sodium hydroxide solution, wherein the solution is changed from brown yellow to light yellow, and after continuously reacting for 10-15h, the solution is changed into dark brown to obtain a gold nanocluster solution;
5) synthesizing a nano gold composite material:
adding the gold nanocluster solution into the aminated mesoporous silica gold nanorod solution, stirring for 8-12h at the rotation speed of 50-150rpm, centrifuging and removing supernatant to obtain lower colloidal solution, and washing with ultrapure water to obtain mauve colloidal solution, thus obtaining the core-shell type nano-gold composite material.
Preferably, the molar ratio of the reaction components in step 1) is CTAB: gold chloride acid: silver nitrate: ascorbic acid: sodium borohydride =80000:40-50: 100-.
Preferably, in the step 2), the mass concentration of the gold nanorod solution is 50-200 ug/ml; the volume percentage concentration of the ethyl orthosilicate methanol solution is 10-20%; the mass ratio of the gold nanorod solution to the tetraethoxysilane is 9: 25-100.
Preferably, the mass ratio of each reaction component in the step 3) is that the mesoporous silica gold nanorod: APTES =25-50: 1.
Preferably, the molar ratio of each reaction component in the step 4) is between bovine serum albumin: gold chloride acid: sodium hydroxide = 100:1-2: 10-12.
Preferably, the volume ratio of each reaction component in the step 5) is that of the aminated mesoporous silica gold nanorods: gold nanoclusters = 10-20: 1.
Preferably, the thickness of the silicon shell with the mesoporous structure formed in the step 2) is 10-20 nm.
The bovine serum albumin is preferably a fifth component of bovine serum albumin.
The core-shell type nano-gold compound prepared by the method takes gold nanorods as a core of a structure, mesoporous silica is coated on the surface of the gold core, and gold nanoclusters are loaded on the surface and in the pores of the mesoporous silica.
The core-shell type nano-gold compound is applied to intelligent nano-drug loading, photo-thermal treatment of cancer and biological imaging.
CTAB is cetyltrimethylammonium bromide.
TEOS is tetraethyl orthosilicate.
APTES is 3-aminopropyl triethoxysilane.
Compared with the prior art, the invention has the following beneficial effects:
(1) the core-shell type nano-gold compound has the characteristics of large specific surface area, large loading capacity and fluorescence.
(2) The core-shell type nano-gold compound can effectively improve the photo-thermal performance and the biocompatibility of the gold nanorods.
(3) The preparation method of the core-shell type nano-gold compound is simple, has a wide application range, and can be used for large-scale production.
Drawings
FIG. 1 is an ultraviolet spectrum of gold nanorods (AuNRs), gold nanoclusters (AuNCs), gold nanorod-wrapped silica (AuNRs @ SiO 2), and silica-wrapped gold nanorod-loaded gold nanoclusters (AuNRs @ SiO2@ AuNCs).
FIG. 2 is a transmission electron microscope image of gold nanorods (AuNRs), gold nanoclusters (AuNCs), gold nanorod-wrapped silica (AuNRs @ SiO 2), and silica-wrapped gold nanorod-loaded gold nanoclusters (AuNRs @ SiO2@ AuNCs).
FIG. 3 is a temperature change diagram of the gold nanorods (AuNRs), gold nanoclusters (AuNCs), gold nanorod-wrapped silica (AuNRs @ SiO 2), and silica-wrapped gold nanorod-loaded gold nanoclusters (AuNRs @ SiO2@ AuNCs) after being irradiated for 5min by 808nm 2.5W laser.
FIG. 4 is a temperature rise curve diagram of the gold nanorods (AuNRs), gold nanoclusters (AuNCs), gold nanorod-wrapped silica (AuNRs @ SiO 2), and silica-wrapped gold nanorod-loaded gold nanoclusters (AuNRs @ SiO2@ AuNCs) under 808nm 2.5W laser irradiation for 5 min.
Fig. 5 is a temperature change curve of the core-shell type nano-gold composite material after continuous laser irradiation.
FIG. 6 is a biocompatibility chart of gold nanorods (AuNRs), gold nanoclusters (AuNCs), gold nanorod-wrapped silica (AuNRs @ SiO 2), and silica-wrapped gold nanorod-loaded gold nanoclusters (AuNRs @ SiO2@ AuNCs) according to the present invention.
FIG. 7 is a fluorescence spectrum of the gold nanorod/core-shell type nano-gold composite material of the invention.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, belong to the scope of the present invention.
A preparation method of a core-shell type nano-gold composite material comprises the following steps:
1) gold nanorod solutions (AuNRs) were prepared by a seedless method:
dissolving CTAB in ultrapure water, sequentially adding a chloroauric acid solution, a silver nitrate solution, an ascorbic acid solution and a sodium borohydride solution, stirring for 10-30s in a water bath at 30-40 ℃, standing for 4-8h, centrifuging at a rotating speed of more than ten thousand revolutions, removing the upper clear liquid to obtain a lower colloidal solution, washing with deionized water, removing the redundant CTAB solution, and taking the lower colloidal solution to obtain a gold nanorod solution;
the molar ratio of each reaction component is CTAB: gold chloride acid: silver nitrate: ascorbic acid: sodium borohydride =80000:40-50: 100-.
Preferably, the molar ratio of the reaction components is CTAB: gold chloride acid: silver nitrate: ascorbic acid: sodium borohydride =80000: 40: 100: 600: 1.5.
the mass concentration of the obtained gold nanorod solution is 50-200 ug/ml;
2) preparation of mesoporous silica-coated gold nanorod solution (AuNRs @ mSiO)2）：
Adding deionized water into the gold nanorod solution obtained in the step 1), performing ultrasonic treatment for 10-20min, then adding a sodium hydroxide solution in a water bath at 30-40 ℃, adjusting the pH value of the solution to 9-10, and rapidly stirring at the rotation speed of 300-500rpm for 20-40 min;
then, under the stirring state, dropwise adding a TEOS methanol solution (preferably a TEOS methanol solution with the mass fraction of 10-20%) for three times, wherein the interval is 20-40min each time; continuously reacting for 30-40h at the rotation speed of 300-500rpm under the stirring state;
the mass ratio of the gold nanorod solution to the TEOS methanol solution with the mass fraction of 10-20% is 9: 25-100.
Finally, centrifuging, washing with water and alcohol respectively to prepare a mesoporous silica gold nanorod solution, and storing in a 4-degree refrigerator; the thickness of the mesoporous structure silicon shell in the mesoporous silicon dioxide gold nanorod is 10-20 nm.
3) Carrying out amination modification (AuNRs @ mSiO) on gold nanorods wrapped by mesoporous silica2-NH2）：
Adding 100ul of APTES (methanol solution) into the mesoporous silica gold nanorod solution obtained in the step 2). Then, adding methanol and hydrochloric acid (adjusting the pH to 1), and heating under reflux for 4-8h at 50-70 ℃ to remove the CTAB template;
centrifuging the refluxed substance, taking the lower layer precipitate to obtain aminated mesoporous silica gold nanorods;
the mass ratio of each reaction component is mesoporous silica gold nanorod: APTES =25-50: 1.
4) Preparation of gold nanocluster solution (AuNCs):
adding a bovine serum albumin (fifth component) solution into a chloroauric acid solution, stirring for 1-5min under a water bath condition of 30-40 ℃, then adding a sodium hydroxide solution, wherein the solution is changed from brown yellow to light yellow, and after continuously reacting for 10-15h, the solution is changed into dark brown to obtain a gold nanocluster solution;
the mol ratio of each reaction component is a fifth component of bovine serum albumin: gold chloride acid: sodium hydroxide = 100:1-2: 10-12.
5) Synthesizing a nano gold composite material:
adding the gold nanocluster solution into the aminated mesoporous silica gold nanorod solution, stirring for 8-12h at the rotation speed of 50-150rpm, centrifuging and removing supernatant to obtain lower colloidal solution, and washing with ultrapure water to obtain mauve colloidal solution, thus obtaining the core-shell type nano-gold composite material.
The volume ratio of each reaction component is that the mesoporous silica gold nanorods are aminated: gold nanoclusters = 10-20: 1.
The core-shell type nano-gold compound prepared by the method takes gold nanorods as a core of a structure, mesoporous silica is coated on the surface of the gold core, and gold nanoclusters are loaded on the surface and in the pores of the mesoporous silica.
CTAB is cetyltrimethylammonium bromide.
TEOS is 20% strength ethyl orthosilicate in methanol.
APTES is 3-aminopropyl triethoxysilane.
The core-shell type nanogold composite can be applied to the aspects of intelligent nano drug loading, photo-thermal treatment of cancer, biological imaging and the like.
The gold nanorods, the gold nanoclusters and the mesoporous silica are combined, so that the composite material has the functions of good biocompatibility, mesoporous structure, fluorescence property and good photo-thermal property, and is an ideal photo-thermal treatment material. The material improves the photo-thermal performance of the gold nanorods and has good application potential in photo-thermal treatment.
The nano-carrier has the fluorescent characteristic, can be used as a multifunctional fluorescent probe, and has great application potential in the aspect of biological imaging adjuvant therapy.
The preparation methods in the following examples are conventional methods unless otherwise specified; the experimental materials used were purchased by conventional biochemical manufacturers unless otherwise specified.
Example 1:
1) gold nanorod solutions (AuNRs) were prepared by a seedless method:
synthesizing a gold nanorod by a seedless method, firstly weighing 1.8218g of CTAB powder, dissolving in 50ml of ultrapure water, and ultrasonically dissolving;
10ml of dissolved CTAB (cetyltrimethyl ammonium bromide) with the concentration of 0.1M is added into a triangular flask, and 208 ul of a 0.024M chloroauric acid solution, 100ul of a 0.01M silver nitrate solution and 60ul of a 0.1M ascorbic acid solution are sequentially added under stirring in a water bath with the temperature of 37 ℃. Then 16ul of 1mM sodium borohydride solution was added and stirred for 25 s. And standing the solution for 6h, centrifuging the solution by using ultrapure water, and removing excessive CTAB to obtain the gold nanorod solution.
The sodium borohydride solution is prepared by using ice water.
2) Preparing gold nanorods wrapped by mesoporous silica,
and (2) performing ultrasonic treatment on the prepared gold nanorods for 15min, adding 10ml of gold nanorods into a triangular flask, stirring in a water bath at 30 ℃, adding 100ul of 0.1M NaOH, reacting for 30min, adding 30ul of TEOS methanol solution with the mass fraction of 20% for three times, reacting for 36h continuously, centrifuging and washing with water and alcohol respectively, and storing in a refrigerator at 4 ℃.
3) Preparing aminated mesoporous silica gold nanorods, and adding 100ul APTES into the prepared mesoporous silica gold nanorod solution. Then, the mixture was added to 40ml of a methanol solution, a hydrochloric acid solution was added to adjust the pH to 1, excess CTAB molecules were removed under reflux heating at 60 degrees, and the mixture was reacted for 6 hours and then centrifuged and washed.
4) Preparing gold nanocluster solution (AuNCs), adding 2ml of 50mg/ml bovine serum albumin fifth component solution into 2ml of 0.012mM chloroauric acid solution, stirring for 2min in a water bath at 30 ℃, adding 2ml of 0.1M sodium hydroxide solution, changing the solution from brown to light yellow, and reacting for 12h to obtain dark brown solution.
5) And (3) synthesizing a nano-gold composite material, adding 2ml of prepared gold nano-cluster solution into 10ml of aminated mesoporous silica gold nanorod solution, slightly stirring for 10 hours, centrifuging by using ultrapure water, and removing supernatant to obtain a purple solution.
The experimental results show that:
FIG. 1 shows gold nanorods (AuNRs), gold nanoclusters (AuNCs) and gold nanorod-wrapped silicon dioxide (AuNRs @ SiO) prepared by seedless method2) Gold nanorod-loaded gold nanocluster (AuNRs @ SiO) wrapped by silicon dioxide2@ AuNCs).
In the ultraviolet spectrum shown in fig. 1, after the gold nanorods are wrapped by the silicon dioxide layer, the refractive index of the surface of the gold nanorods is changed, so that the ultraviolet spectrum is subjected to blue shift, and after the gold nanoclusters are loaded, the peak position of the gold nanorods is subjected to red shift, which indicates that the gold nanoclusters are loaded on the silicon shell.
In FIG. 2, A is gold nanorod-wrapped silica (AuNRs @ SiO)2) The TEM image and B are gold nano-rod loaded gold nano-clusters (AuNRs @ SiO) wrapped by silicon dioxide2@ AuNCs).
The image A in FIG. 2 shows that the synthesized gold nanorods (AuNRs) have uniform size (40 nm), the image B in FIG. 2 shows that the synthesized gold nanoclusters (AuNCs) have size below 2nm, the image C in FIG. 2 shows that the gold nanorods (with thickness about 10-20 nm) are successfully wrapped by silicon dioxide, and the image D in FIG. 2 shows that the gold nanoclusters are loaded on a silicon shell, so that the synthesis is completed.
FIG. 3 shows that after 808nm 2.5W laser irradiation for 5min, gold nanorods (AuNRs), gold nanoclusters (AuNCs) and gold nanorods wrap silicon dioxide (AuNRs @ SiO)2) Gold nanorod-loaded gold nanocluster (AuNRs @ SiO) wrapped by silicon dioxide2@ AuNCs).
As can be seen from the figure, AuNRs @ SiO2@ AuNCs has very excellent lightThe thermal performance is improved by more than 50 percent compared with the photo-thermal heating performance of the gold nanorods.
FIG. 4 shows that after 808nm 2.5W laser irradiation for 5min, gold nanorods (AuNRs), gold nanoclusters (AuNCs) and gold nanorods wrap silicon dioxide (AuNRs @ SiO)2) Gold nanorod-loaded gold nanocluster (AuNRs @ SiO) wrapped by silicon dioxide2@ AuNCs).
As can be clearly seen in the figure, AuNRs' temperature rise of 12.3 ℃ in 300s is AuNRs @ SiO2Temperature rise of @ AuNCs at 32.9 ℃ within 300s shows AuNRs @ SiO relative to AuNRs2The heating speed of @ AuNCs is greatly improved.
FIG. 5 shows the core-shell nanogold composite (AuNRs @ SiO) of the invention2@ AuNCs) temperature change curve after continuous laser irradiation.
As shown in the figure, the film still has good photo-thermal performance after continuous illumination, which shows that AuNRs @ SiO2@ AuNCs has good photo-thermal stability.
FIG. 6 shows gold nanorods (AuNRs) and gold nanorod-wrapped silica (AuNRs @ SiO)2) Gold nanorod-loaded gold nanocluster (AuNRs @ SiO) wrapped by silicon dioxide2@ AuNCs).
As shown in the figure, AuNRs @ SiO2@ AuNCs have good biocompatibility.
FIG. 7 is a fluorescence spectrum of gold nanorods and gold nanoclusters loaded on the gold nanorods coated with silicon dioxide.
In the figure, after loading the gold nanoclusters, the strong emission peak of the fluorescence spectrum of the gold nanoclusters at 690nm is shifted to 680nm from the left, and the intensity of the emission peak is still very high, which shows that the gold nanorods wrapped by the silicon dioxide still have the fluorescence property of the gold nanoclusters after loading the gold nanoclusters, and the fluorescence of the gold nanoclusters is prevented from being quenched by the gold nanorods.
Example 2:
1) preparation of gold nanorod solution
Synthesizing a gold nanorod by a seedless method, firstly weighing 1.8218g of CTAB powder, dissolving in 50ml of ultrapure water, and ultrasonically dissolving; 10ml of dissolved CTAB (cetyltrimethyl ammonium bromide) with the concentration of 0.1M is added into a triangular flask, and 208 ul of a 0.024M chloroauric acid solution, 100ul of a 0.01M silver nitrate solution and 60ul of a 0.1M ascorbic acid solution are sequentially added under stirring in a water bath with the temperature of 37 ℃. Then 16ul of 1mM sodium borohydride solution (in ice water) was added and stirred for 25 s. And standing the solution for 6h, centrifuging the solution by using ultrapure water, and removing excessive CTAB to obtain the gold nanorod solution.
2) Preparing a gold nanorod coated with mesoporous silica, performing ultrasonic treatment on the prepared gold nanorod for 15min, adding 10ml of the gold nanorod into a triangular flask, stirring in a water bath at 30 ℃, adding 100ul of 0.1M NaOH for reaction for 30min, adding 40ul of TEOS (20% methanol) for three times, performing reaction for 36h, performing centrifugal washing with water and alcohol respectively, and storing in a refrigerator at 4 ℃.
3) Preparing aminated mesoporous silica gold nanorods, and adding 100ul APTES into the prepared mesoporous silica gold nanorod solution. Then, the mixture was added to 40ml of a methanol solution, a hydrochloric acid solution was added to adjust the pH to 1, excess CTAB molecules were removed under reflux heating at 60 degrees, and the mixture was reacted for 6 hours and then centrifuged and washed.
4) Preparing gold nanocluster solution (AuNCs), adding 2ml of 50mg/ml bovine serum albumin (fifth component) solution into 2ml of 0.012mM chloroauric acid solution, stirring for 2min in a water bath at 30 ℃, adding 2ml of 0.1M sodium hydroxide solution, changing the solution from brown to light yellow, and reacting for 12h to obtain dark brown solution.
5) And (3) synthesizing a nano-gold composite material, adding 2ml of prepared gold nano-cluster solution into 10ml of aminated mesoporous silica gold nanorod solution, slightly stirring for 10 hours, centrifuging by using ultrapure water, and removing supernatant to obtain a purple solution.
Example 3:
1) preparation of gold nanorod solution
Synthesizing a gold nanorod by a seedless method, firstly weighing 1.8218g of CTAB powder, dissolving in 50ml of ultrapure water, and ultrasonically dissolving; 10ml of dissolved CTAB (cetyltrimethyl ammonium bromide) with the concentration of 0.1M is added into a triangular flask, and 208 ul of a 0.024M chloroauric acid solution, 100ul of a 0.01M silver nitrate solution and 60ul of a 0.1M ascorbic acid solution are sequentially added under stirring in a water bath with the temperature of 37 ℃. Then 16ul of 1mM sodium borohydride solution (in ice water) was added and stirred for 25 s. And standing the solution for 6h, centrifuging the solution by using ultrapure water, and removing excessive CTAB to obtain the gold nanorod solution.
2) Preparing gold nanocluster solution (AuNCs), adding 2ml of 50mg/ml bovine serum albumin (fifth component) solution into 2ml of 0.012mM chloroauric acid solution, stirring for 2min in a water bath at 30 ℃, adding 2ml of 0.1M sodium hydroxide solution, changing the solution from brown to light yellow, and reacting for 12h to obtain dark brown solution.
3) Mixing the synthesized gold nanocluster solution and the gold nanorod solution, performing ultrasonic treatment for 15min, adding 10ml of the mixture into a triangular flask, stirring in a water bath at 30 ℃, adding 100ul of 0.1M NaOH for reaction for 30min, adding 40ul of TEOS (20% methanol) for three times, performing reaction for 36h continuously, performing centrifugal washing with water and alcohol respectively, and storing in a refrigerator at 4 ℃.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to limit the present invention, and those skilled in the art can make variations and modifications of the present invention without departing from the spirit and scope of the present invention by using the methods and technical contents disclosed above.
Claims (9)
1. The preparation method of the core-shell type nano-gold composite material is characterized by comprising the following steps:
1) preparing a gold nanorod solution by a seed-free method:
dissolving CTAB in ultrapure water, sequentially adding a chloroauric acid solution, a silver nitrate solution, an ascorbic acid solution and a sodium borohydride solution, stirring for 10-30s in a water bath at 30-40 ℃, standing for 4-8h, centrifuging, removing an upper clear liquid to obtain a lower colloidal solution, washing with deionized water, removing the redundant CTAB solution, and taking the lower colloidal solution to obtain a gold nanorod solution;
2) preparing a gold nanorod solution wrapped by mesoporous silica:
adding deionized water into the gold nanorod solution obtained in the step 1), performing ultrasonic treatment for 10-20min, adjusting the pH value of the solution to 9-10 in a water bath at 30-40 ℃, and rapidly stirring for 20-40 min;
then, dropwise adding a methanol solution of ethyl orthosilicate for three times, wherein the interval is 20-40min each time; continuously reacting for 30-40h under the stirring state;
finally, centrifuging, and washing with water and alcohol respectively to prepare a mesoporous silica gold nanorod solution;
3) carrying out amination modification on the gold nanorods wrapped by the mesoporous silica:
adding the mesoporous silica gold nanorod solution obtained in the step 2) into an APTES solution;
then, adding methanol and hydrochloric acid, heating under reflux for 4-8h at 50-70 ℃, and removing the CTAB template;
centrifuging the refluxed substance, taking the lower layer precipitate to obtain aminated mesoporous silica gold nanorods;
4) preparing a gold nanocluster solution:
adding a bovine serum albumin solution into a chloroauric acid solution, stirring for 1-5min under the condition of a water bath at 30-40 ℃, then adding a sodium hydroxide solution, wherein the solution is changed from brown yellow to light yellow, and after continuously reacting for 10-15h, the solution is changed into dark brown to obtain a gold nanocluster solution;
5) synthesizing a nano gold composite material:
adding the gold nanocluster solution into the aminated mesoporous silica gold nanorod solution, stirring for 8-12h at the rotation speed of 50-150rpm, centrifuging and removing supernatant to obtain lower colloidal solution, and washing with ultrapure water to obtain mauve colloidal solution, thus obtaining the core-shell type nano-gold composite material.
2. The method for preparing the core-shell type nano-gold composite material according to claim 1, wherein the molar ratio of each reaction component in the step 1) is CTAB: gold chloride acid: silver nitrate: ascorbic acid: sodium borohydride =80000:40-50: 100-.
3. The method for preparing the core-shell nano-gold composite material according to claim 1, wherein in the step 2), the mass concentration of the gold nanorod solution is 50-200 ug/ml; the volume percentage concentration of the ethyl orthosilicate methanol solution is 10-20%; the mass ratio of the gold nanorod solution to the tetraethoxysilane is 9: 25-100.
4. The method for preparing the core-shell type nano-gold composite material according to claim 1, wherein the mass ratio of each reaction component in the step 3) is that the mesoporous silica gold nanorod: APTES =25-50: 1.
5. The method according to claim 1, wherein the molar ratio of the reaction components in step 4) is between bovine serum albumin: gold chloride acid: sodium hydroxide = 100:1-2: 10-12.
6. The method for preparing the core-shell type nano-gold composite material according to claim 1, wherein the volume ratio of the reaction components in the step 5) is that of the aminated mesoporous silica gold nanorods: gold nanoclusters = 10-20: 1.
7. The method of claim 1, wherein the silica shell having a mesoporous structure formed in step 2) has a thickness of 10-20 nm.
8. The core-shell type nano-gold composite material prepared by the method of any one of claims 1 to 7 is characterized in that gold nanorods are used as a core of a structure, mesoporous silica is coated on the surface of the gold core, and gold nanoclusters are loaded on the surface and in the pores of the mesoporous silica.
9. The use of the core-shell nanogold composite of claim 8 for intelligent drug-loaded nanomedicines, photothermal therapy of cancer and bioimaging.
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