Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a silver-coated gold nanorod, which comprises the following steps:
preparation of NaBH4Dissolving and reacting said NaBH4The solution was inserted into ice for at least 10 minutes;
adding a CTAB solution of hexadecyl trimethyl ammonium bromide into a container, placing the container in a water bath at 30 ℃, and stirring the mixture at a speed of not higher than 600 rpm;
adding HAuCl into the CTAB solution4Solution, then adding said NaBH under vigorous stirring at not less than 1000rpm4Obtaining a brown seed solution; and
after 5 minutes, the seed solution was allowed to stand in a water bath for 1 hour;
adding AgNO into CTAB solution under stirring at 30 deg.C not higher than 600rpm3Aqueous solution, then HAuCl is added4The solution, ascorbic acid solution and seed solution to obtain colorless mixed solution;
stirring the colorless mixed solution for 1 minute, and then standing in the dark for 1 hour;
transferring the mixed solution after standing to an Eppendorf tube, and centrifuging to remove supernatant to obtain solution precipitate;
resuspending the solution precipitate in phosphate buffer saline to obtain gold nanorods; and
and forming a silver coating on the surface of the gold nanorod.
In one embodiment of the invention, the NaBH4The concentration of the solution is 0.01Mol/L, the concentration of the CTAB solution is 0.1Mol/L, and the HAuCl4The concentration of the solution was 0.01 Mol/L.
In one embodiment of the invention, the seed solution comprises 9.75ml CTAB solution, 0.25ml HAuCl4Solution and 0.6ml NaBH4And (3) solution.
In one embodiment of the invention, the AgNO3The concentration of the aqueous solution was 0.01Mol/L and the concentration of the ascorbic acid was 0.1 Mol/L.
In one embodiment of the invention, the gold nanorods comprise 130 μ l of AgNO3Aqueous solution, 9.5ml CTAB solution, 0.5ml HAuCl4Solution, 55. mu.l ascorbic acid, and 12. mu.l seed solution.
In one embodiment of the invention, the centrifugation speed is 8500rpm and lasts 15 minutes.
In one embodiment of the invention, the forming of the silver coating on the surface of the gold nanorod comprises adding silver nitrate and ascorbic acid solutions with different concentrations into the gold nanorod solution, then adding ammonia water, and mixing uniformly until the color does not change any more, so that the surface of the gold nanorod is coated with the silver layer.
In one embodiment of the invention, the transfer is to a 2mL centrifuge tube. To 0.5mL of the prepared gold nanorod solution was added 7.5. mu.L of 0.1M AgNO3And 0.1M ascorbic acid, followed by 3. mu.LNH4OH, AgNO reduction by ascorbic acid3The mixture was blackened, and the solution was centrifuged at 4000rpm for 10 minutes at 4 ℃ and then redispersed in ultrapure water.
In one embodiment of the invention, 7.5. mu.L of 0.1M AgNO was added3And 0.1M ascorbic acid can be added in multiple portions, with 10s vortexing after each addition.
The embodiment of the invention provides a method for synthesizing silver-coated gold nanorods. The gold nanorod coated with silver has stronger SERS performance. The surface of the formed silver-coated gold nanorod is free of surfactant, free of biotoxicity and good in biocompatibility. The synthesis method of the silver-coated gold nanorod provided by the invention has the advantages of simplicity in operation, rapidness, strong repeatability, low cost and the like.
Detailed Description
In the following description, the invention is described with reference to various embodiments. One skilled in the relevant art will recognize, however, that the embodiments may be practiced without one or more of the specific details, or with other alternative and/or additional methods, materials, or components. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of embodiments of the invention. Similarly, for purposes of explanation, specific numbers, materials and configurations are set forth in order to provide a thorough understanding of the embodiments of the invention. However, the invention may be practiced without specific details. Further, it should be understood that the embodiments shown in the figures are illustrative representations and are not necessarily drawn to scale.
Reference in the specification to "one embodiment" or "the embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment.
The embodiment of the invention discloses a method for synthesizing silver-coated gold nanorods. The gold nanorod particles solve the problem of CTAB cytotoxicity on the surfaces of the gold nanorods through silver coating, so that the gold nanorods have better biocompatibility and can maintain the stability of the gold nanorods, and meanwhile, the gold nanorods have stronger SERS (surface enhanced Raman scattering) characteristics due to the silver coating, so that the silver-coated gold nanorods can obtain a larger space in the application of biomedicine, such as biosensors, biomedical imaging, medical rapid detection and the like.
Fig. 1 illustrates a method for preparing silver-coated gold nanorods according to one embodiment of the present invention.
As shown in fig. 1, a seed solution is first prepared, comprising:
first, at step 1011, NaBH is prepared4And (3) solution. Preparation of NaBH at defined concentrations4Dissolving and reacting said NaBH4The solution was inserted into ice for at least 10 minutes; in one embodiment of the invention, the NaBH4The concentration of the solution is 0.01 Mol/L;
next, in step 1012, a CTAB solution is prepared. The CTAB solution is cetyltrimethylammonium bromide (Cetrimonium bromide), and is prepared by: adding a certain amount of CTAB solution of a protective agent with a specified concentration into a container, wherein the volume of the container is not less than 20mL, and the container can be a glass vial, a beaker or any other container convenient for stirring, and placing the container in a water bath with the temperature of 30 ℃ to slowly stir at the speed of not more than 600 rpm; in one embodiment of the invention, the concentration of CTAB solution is 0.1Mol/L, in another embodiment of the invention, CTAB solution is prepared in 9.75 ml;
next, at step 1013, a seed solution is synthesized. Adding HAuCl into the CTAB solution4The solution is then added with vigorous stirring at not less than 1000rpm to the NaBH prepared in step 10114Obtaining a seed solution, wherein the color of the solution is changed from bright yellow to dark brown in the process; in one embodiment of the invention, the HAuCl4The solution concentration was 0.01Mol/L, and in yet another embodiment of the invention, HAuCl was used40.25ml of solution and NaBH40.6ml of solution; and
finally, at step 1014, rest. After the solution prepared in step 1013 became tan for 5 minutes, the seed solution was allowed to stand in a water bath for 1 hour; and
synthesizing gold nanorods comprising:
first, at step 1021, the solution is mixed. AgNO is slowly stirred at a speed of not higher than 600rpm at a temperature of 30 DEG C3The aqueous solution was added to CTAB solution, followed by HAuCl4The solution, the ascorbic acid solution and the seed solution are added, and the color of the solution is changed from fresh yellow to colorless; in one embodiment of the invention, the AgNO3The concentration of the aqueous solution is 0.01Mol/L, the concentration of the CTAB solution is 0.1Mol/L, and the HAuCl4The concentration of the solution was 0.01Mol/L and the concentration of the ascorbic acid was 0.1Mol/L, and in yet another embodiment of the invention, the respective solutions were used in the following amounts: 30 μ l of AgNO3Aqueous solution, 9.5ml CTAB solution, 0.5ml HAuCl4Solution, 55. mu.l ascorbic acid, and 12. mu.l seed solution;
next, at step 1022, the solution is stirred. Stirring the colorless mixed solution obtained in the step 1021 for 1 minute, standing for 1 hour in the dark, and changing the color to red in about 15 minutes, which indicates that the synthesis of the gold nanorods is successful;
next, at step 1023, a precipitate is obtained. Transferring the mixed solution into an Eppendorf tube, centrifuging, and removing a supernatant to obtain a solution precipitate; in one embodiment of the invention, the centrifugation speed is 8500rpm for 15 minutes; and
finally, at step 1024, gold nanorods are obtained and stored. Resuspending the solution precipitate in phosphate buffer saline to obtain gold nanorods, and storing the gold nanorods at room temperature; in one embodiment of the invention, the solution pellet is resuspended in 10ml of phosphate buffered saline at pH 7.4;
next, in step 1031, a silver coating is formed on the surface of the gold nanorods. Specifically, silver nitrate and ascorbic acid solutions with different concentrations are added into a gold nanorod solution, then ammonia water is added, and the mixture is uniformly mixed until the color does not change any more, so that the surface of a gold nanorod is coated with a silver layer, and the silver-coated gold nanorod solution is obtained.
For example, in one example, 0.5mL of a previously prepared gold nanorod solution is transferred to a 2mL centrifuge tube. Add 7.5. mu.L of 0.1M AgNO to the tube3And 0.1M Ascorbic Acid (AA). Multiple additions were made, with 10s vortexing after each addition. Then 3. mu.L NH was added4OH, AgNO reduction by ascorbic acid AA3The mixture turns black. The solution will stabilize in about 5 minutes. Finally, the solution was centrifuged at 4000rpm for 10 minutes at 4 ℃ and then redispersed in ultrapure water.
Next, the silver coating layer of the gold nanorods was studied by using ultraviolet-visible light (UV-Vis) absorption spectroscopy and TEM transmission electron microscopy.
FIG. 2 shows a TEM image of a gold nanorod formed by an embodiment of the present invention.
Fig. 3 shows a transmission electron microscope TEM image of silver-coated gold nanorods formed by an embodiment of the present invention. As shown in fig. 3, the gold nanorods were completely covered with silver, and the particle diameter became larger after the surface of the gold nanorods was covered with silver.
Rhodamine 6G (R6G) was used as a model analyte to test the surface raman enhancement performance of gold nanorods and silver-coated gold nanorods. Fig. 4 shows a Surface Enhanced Raman Spectrum (SERS) of a 1 μ M solution into which gold nanorods formed by an embodiment of the present invention were dropped on a glass slide. Fig. 5 shows a Surface Enhanced Raman Spectrum (SERS) of a 1 μ M solution into which silver-coated gold nanorods formed by an example of the present invention were dropped on a glass slide. As can be seen from fig. 4 and 5, the signal intensity from the silver-coated gold nanorods is an order of magnitude higher than that of the gold nanorods.
The embodiment of the invention provides a method for synthesizing silver-coated gold nanorods. The gold nanorod coated with silver has stronger SERS performance. The surface of the formed silver-coated gold nanorod is free of surfactant, free of biotoxicity and good in biocompatibility. The synthesis method of the silver-coated gold nanorod provided by the invention has the advantages of simplicity in operation, rapidness, strong repeatability, low cost and the like.
While various embodiments of the present invention have been described above, it should be understood that they have been presented by way of example only, and not limitation. It will be apparent to persons skilled in the relevant art that various combinations, modifications, and changes can be made thereto without departing from the spirit and scope of the invention. Thus, the breadth and scope of the present invention disclosed herein should not be limited by any of the above-described exemplary embodiments, but should be defined only in accordance with the following claims and their equivalents.