Preparation method and application of gold and silver nanoflower particles with core-shell structure

Abstract

The invention relates to the technical field of preparation of gold and silver nanoflower particles, in particular to a preparation method of gold and silver nanoflower particles with a core-shell structure, which comprises the following steps: preparing polylysine powder, accurately weighing 0.4 g of polylysine powder, selecting 40ml of ultrapure water as a solvent, adding the weighed polylysine powder into the ultrapure water, and stirring uniformly to obtain the gold and silver nanoflower particles with the core-shell structure. Then an ultrasonic dissolution method is used to finally obtain a 1.0 wt% polylysine solution for subsequent use; the ascorbic acid solution is used as a reducing agent to separate gold molecules and silver molecules in the chloroauric acid solution and the silver nitrate solution in the solution independently, and the polylysine solution is used as a stabilizer to enable the gold molecules to be attached to the surfaces of the silver molecules to form gold and silver nanoflower particles. Gold molecules and silver molecules reduced by ascorbic acid can be controlled by silver nitrate, and the final particle size and shape of gold and silver nanoflower particles can be changed by changing the amount of silver nitrate.

Description

Technical Field

[0001] The invention relates to the technical field of gold-silver nano-flower particle preparation, in particular to a method for preparing gold-silver nano-flower particles with a core-shell structure and application thereof. Background Art

[0002] Gold and silver nanoflower particles are a new type of nanomaterial, and their preparation methods and applications have been widely studied in recent years. This type of nanoparticle usually has unique optical, electrical and chemical properties, so it has potential application value in many fields. Gold and silver nanoflower particles of different concentrations can quickly absorb light energy to generate heat under laser irradiation, causing the water temperature to rise rapidly. This characteristic makes gold and silver nanoflower particles promising for photothermal therapy.

[0003] At present, the preparation of gold and silver nanoflower particles is to fix gold molecules on the surface of silver molecules through redox reaction. However, in the microscopic environment, the particle size and shape of the gold molecules fixed on the surface of the silver molecules cannot be controlled, which will lead to the uncontrollable particle size and shape of the gold and silver nanoflower particles at the preparation site. The particle size and shape of the gold and silver nanoflower particles will affect their own light energy absorption rate and reserves. When the particle size and shape of the prepared gold and silver nanoflower particles cannot be controlled, their usage characteristics cannot be maintained stable, and they cannot be used as a stable therapeutic agent. Summary of the invention

[0004] In view of the problems in the prior art, the present invention provides a method for preparing gold-silver nanoflower particles with a core-shell structure and application thereof.

[0005] The technical solution adopted by the present invention to solve the technical problem is: a method for preparing gold-silver nanoflower particles with a core-shell structure, the preparation method comprising the following steps: Step 1: First, prepare polylysine powder, accurately weigh 0.4 g of polylysine powder, select 40 ml of ultrapure water as a solvent, add the weighed polylysine powder into the ultrapure water, and then use an ultrasonic dissolution method to finally obtain a 1.0 wt% polylysine solution for subsequent use; Step 2: Take 4 ml of the previously prepared 1.0 wt% polylysine solution, and then measure 36 ml of ultrapure water, add 4 ml of the 1.0 wt% polylysine solution to 36 ml of ultrapure water, and perform ultrasonic dissolution again. Through this dilution method, a 0.1 wt% polylysine solution is obtained for the next reaction; Step 3, taking out 4 ml from the 0.1wt% polylysine solution, and then preparing 36 ml of ultrapure water, adding 4 ml of the 0.1wt% polylysine solution into 36 ml of ultrapure water, and dissolving by ultrasonication to obtain a 0.01wt% polylysine solution; Step 4, weigh 0.01g of silver nitrate particles, select 10ml of ultrapure water as a solvent, add the weighed silver nitrate particles into the ultrapure water, use ultrasonic dissolution to completely dissolve the silver nitrate in the ultrapure water, obtain a silver nitrate solution with a concentration of 6mmol / L, and store it for subsequent reactions; Step 5, weigh 0.176 g of ascorbic acid powder, take 10 ml of ultrapure water, add the ascorbic acid powder to the ultrapure water, and dissolve it by ultrasound to obtain a 0.1 mol / L ascorbic acid solution, which will react with other reagents in the subsequent reaction; Step 6, weigh 1 g of chloroauric acid trihydrate powder, measure 80 ml of deionized water, add the weighed chloroauric acid trihydrate powder into the deionized water, and perform ultrasonic dissolution operation to obtain a 1 wt% chloroauric acid solution for subsequent reaction process; Step 7, take 50 μl of 0.1wt% polylysine solution, add it to a glass reaction bottle filled with 10 ml of ultrapure water, stir the solution in the reaction bottle at room temperature for 2 min, then add 75 μl of 1wt% chloroauric acid solution, and continue stirring for 2 min to fully mix the polylysine solution and the chloroauric acid solution and undergo a preliminary reaction, then add 30 μl of 6mmol / L silver nitrate solution, and then quickly add 40 μl of 0.1mol / L ascorbic acid solution within 45 s. When adding the ascorbic acid solution, it needs to be completed in a short time, which helps to control the progress of the reaction. At this time, it can be observed that the solution quickly changes from colorless to blue, indicating that the reaction is ongoing and new substances are generated. After continuing the reaction for 10 min, stirring is stopped to obtain the product prepared in this embodiment.

[0006] Specifically, the polylysine may play the role of a template or stabilizer. The polylysine solution is gradually diluted during the preparation process in order to control the stabilizing effect of the polylysine solution. The low concentration of polylysine solution can provide a stable reaction environment for subsequent reactions, which helps the directional progress of the reaction of gold molecules attaching to the surface of silver molecules.

[0007] Specifically, the silver nitrate is an oxidant. In the reaction system with ascorbic acid and other substances, the silver molecules in the silver nitrate are precipitated and used as a stabilizing core. At the same time, the silver nitrate can affect the reduction process of the gold ions, so that the separated gold molecules are affected, and the particle size and shape of the gold molecules can be controlled. By changing the amount of silver nitrate, the final particle size and shape of the gold-silver nanoflower particles can be changed.

[0008] Specifically, the ascorbic acid is a reducing agent, which can provide electrons in the reaction system and react with oxidants such as silver nitrate. The reducing effect of ascorbic acid may help to reduce the gold ions and silver ions in the chloroauric acid solution and the silver nitrate solution into gold molecules and silver molecules, and the gold molecules and silver molecules exist in the form of nanoparticles.

[0009] Specifically, the gold acid is the source of gold. During the reaction, the gold ions in the chloroauric acid are reduced under the action of a reducing agent such as ascorbic acid, thereby forming gold-related components in the final product, which may be gold nanoparticles or other gold compound forms, and are indispensable substances for preparing the target product.

[0010] An application of gold-silver nanoflower particles with a core-shell structure, and the application of the gold-silver nanoflower particles in the field of biosensing or medical diagnosis.

[0011] Beneficial effects of the present invention: The invention discloses a method for preparing gold-silver nano-flower particles with a core-shell structure and an application thereof. The method comprises the following steps: taking 50 μl of a 0.1 wt% poly-lysine solution, adding the poly-lysine solution to a glass reaction bottle containing 10 ml of ultrapure water, stirring the solution in the reaction bottle at room temperature, adding 75 μl of a 1 wt% chloroauric acid solution to stir the solution, reacting the poly-lysine solution with the chloroauric acid solution, adding 30 μl of a 6 mmol / L silver nitrate solution, and then quickly adding 40 μl of a 0.1 mol / L ascorbic acid solution within 45 seconds. The ascorbic acid solution is used as a reducing agent to precipitate gold molecules and silver molecules in the chloroauric acid solution and the silver nitrate solution separately in the solution. The poly-lysine solution is used as a stabilizer to cause the gold molecules to adhere to the surface of the silver molecules to form gold-silver nano-flower particles. The gold molecules and silver molecules reduced by ascorbic acid can be controlled by the silver nitrate. The final particle size and shape of the gold-silver nano-flower particles can be changed by changing the amount of the silver nitrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] The present invention is further described below in conjunction with the accompanying drawings and embodiments.

[0013] Figure 1 A flow chart of a method for preparing gold-silver nanoflower particles with a core-shell structure and applications provided by the present invention. DETAILED DESCRIPTION

[0014] In order to make the technical means, creative features, objectives and effects achieved by the present invention easy to understand, the present invention is further explained below in conjunction with specific implementation methods.

[0015] like Figure 1 As shown, a method for preparing gold-silver nanoflower particles with a core-shell structure of the present invention is as follows: Example 1 A preparation method and application of gold-silver nanoflower particles with a core-shell structure, the preparation method comprising the following steps: Step 1: First, prepare polylysine powder, accurately weigh 0.4 g of polylysine powder, select 40 ml of ultrapure water as a solvent, add the weighed polylysine powder into the ultrapure water, and then use an ultrasonic dissolution method to finally obtain a 1.0 wt% polylysine solution for subsequent use; Step 2: Take 4 ml of the previously prepared 1.0 wt% polylysine solution, and then measure 36 ml of ultrapure water, add 4 ml of the 1.0 wt% polylysine solution to 36 ml of ultrapure water, and perform ultrasonic dissolution again. Through this dilution method, a 0.1 wt% polylysine solution is obtained for the next reaction; Step 3, taking out 4 ml from the 0.1wt% polylysine solution, and then preparing 36 ml of ultrapure water, adding 4 ml of the 0.1wt% polylysine solution into 36 ml of ultrapure water, and dissolving by ultrasonication to obtain a 0.01wt% polylysine solution; Step 4, weigh 0.01g of silver nitrate particles, select 10ml of ultrapure water as a solvent, add the weighed silver nitrate particles into the ultrapure water, use ultrasonic dissolution to completely dissolve the silver nitrate in the ultrapure water, obtain a silver nitrate solution with a concentration of 6mmol / L, and store it for subsequent reactions; Step 5, weigh 0.176 g of ascorbic acid powder, take 10 ml of ultrapure water, add the ascorbic acid powder to the ultrapure water, and dissolve it by ultrasound to obtain a 0.1 mol / L ascorbic acid solution, which will react with other reagents in the subsequent reaction; Step 6, weigh 1 g of chloroauric acid trihydrate powder, measure 80 ml of deionized water, add the weighed chloroauric acid trihydrate powder into the deionized water, and perform ultrasonic dissolution operation to obtain a 1 wt% chloroauric acid solution for subsequent reaction process; Step 7, take 50 μl of 0.1wt% polylysine solution, add it to a glass reaction bottle filled with 10 ml of ultrapure water, stir the solution in the reaction bottle at room temperature for 2 min, then add 75 μl of 1wt% chloroauric acid solution, and continue stirring for 2 min to fully mix the polylysine solution and the chloroauric acid solution and undergo a preliminary reaction, then add 30 μl of 6mmol / L silver nitrate solution, and then quickly add 40 μl of 0.1mol / L ascorbic acid solution within 45 s. When adding the ascorbic acid solution, it needs to be completed in a short time, which helps to control the progress of the reaction. At this time, it can be observed that the solution quickly changes from colorless to blue, indicating that the reaction is ongoing and new substances are generated. After continuing the reaction for 10 min, stirring is stopped to obtain the product prepared in this embodiment.

[0016] Specifically, the polylysine may play the role of a template or stabilizer. The polylysine solution is gradually diluted during the preparation process in order to control the stabilizing effect of the polylysine solution. The low concentration of polylysine solution can provide a stable reaction environment for subsequent reactions, which helps the directional progress of the reaction of gold molecules attaching to the surface of silver molecules.

[0017] Specifically, the silver nitrate is an oxidant. In the reaction system with ascorbic acid and other substances, the silver molecules in the silver nitrate are precipitated and used as a stabilizing core. At the same time, the silver nitrate can affect the reduction process of the gold ions, so that the separated gold molecules are affected, and the particle size and shape of the gold molecules can be controlled. By changing the amount of silver nitrate, the final particle size and shape of the gold-silver nanoflower particles can be changed.

[0018] Specifically, the ascorbic acid is a reducing agent, which can provide electrons in the reaction system and react with oxidants such as silver nitrate. The reducing effect of ascorbic acid may help to reduce the gold ions and silver ions in the chloroauric acid solution and the silver nitrate solution into gold molecules and silver molecules, and the gold molecules and silver molecules exist in the form of nanoparticles.

[0019] Specifically, the gold acid is the source of gold. During the reaction, the gold ions in the chloroauric acid are reduced under the action of a reducing agent such as ascorbic acid, thereby forming gold-related components in the final product, which may be gold nanoparticles or other gold compound forms, and are indispensable substances for preparing the target product.

[0020] An application of gold-silver nanoflower particles with a core-shell structure, and the application of the gold-silver nanoflower particles in the field of biosensing or medical diagnosis.

[0021] Example 2 A preparation method and application of gold-silver nanoflower particles with a core-shell structure, the preparation method comprising the following steps: Step 1: First, prepare polylysine powder, accurately weigh 0.4 g of polylysine powder, select 40 ml of ultrapure water as a solvent, add the weighed polylysine powder into the ultrapure water, and then use an ultrasonic dissolution method to finally obtain a 1.0 wt% polylysine solution for subsequent use; Step 2: Take 4 ml of the previously prepared 1.0 wt% polylysine solution, and then measure 36 ml of ultrapure water, add 4 ml of the 1.0 wt% polylysine solution to 36 ml of ultrapure water, and perform ultrasonic dissolution again. Through this dilution method, a 0.1 wt% polylysine solution is obtained for the next reaction; Step 3, taking out 4 ml from the 0.1wt% polylysine solution, and then preparing 36 ml of ultrapure water, adding 4 ml of the 0.1wt% polylysine solution into 36 ml of ultrapure water, and dissolving by ultrasonication to obtain a 0.01wt% polylysine solution; Step 4, weigh 0.02g of silver nitrate particles, select 10ml of ultrapure water as a solvent, add the weighed silver nitrate particles into the ultrapure water, use ultrasonic dissolution to completely dissolve the silver nitrate in the ultrapure water, obtain a silver nitrate solution with a concentration of 12mmol / L, and store it for subsequent reactions; Step 5, weigh 0.176 g of ascorbic acid powder, take 10 ml of ultrapure water, add the ascorbic acid powder to the ultrapure water, and dissolve it by ultrasound to obtain a 0.1 mol / L ascorbic acid solution, which will react with other reagents in the subsequent reaction; Step 6, weigh 1 g of chloroauric acid trihydrate powder, measure 80 ml of deionized water, add the weighed chloroauric acid trihydrate powder into the deionized water, and perform ultrasonic dissolution operation to obtain a 1 wt% chloroauric acid solution for subsequent reaction process; Step 7, take 50 μl of 0.1wt% polylysine solution, add it to a glass reaction bottle filled with 10 ml of ultrapure water, stir the solution in the reaction bottle at room temperature for 2 min, then add 75 μl of 1wt% chloroauric acid solution, and continue stirring for 2 min to fully mix the polylysine solution and the chloroauric acid solution and undergo a preliminary reaction, then add 30 μl of 6mmol / L silver nitrate solution, and then quickly add 40 μl of 0.1mol / L ascorbic acid solution within 45 s. When adding the ascorbic acid solution, it needs to be completed in a short time, which helps to control the progress of the reaction. At this time, it can be observed that the solution quickly changes from colorless to blue, indicating that the reaction is ongoing and new substances are generated. After continuing the reaction for 10 min, stirring is stopped to obtain the product prepared in this embodiment.

[0022] Specifically, the polylysine may play the role of a template or stabilizer. The polylysine solution is gradually diluted during the preparation process in order to control the stabilizing effect of the polylysine solution. The low concentration of polylysine solution can provide a stable reaction environment for subsequent reactions, which helps the directional progress of the reaction of gold molecules attaching to the surface of silver molecules.

[0023] Specifically, the silver nitrate is an oxidant. In the reaction system with ascorbic acid and other substances, the silver molecules in the silver nitrate are precipitated and used as a stabilizing core. At the same time, the silver nitrate can affect the reduction process of the gold ions, so that the separated gold molecules are affected, and the particle size and shape of the gold molecules can be controlled. By changing the amount of silver nitrate, the final particle size and shape of the gold-silver nanoflower particles can be changed.

[0024] Specifically, the ascorbic acid is a reducing agent, which can provide electrons in the reaction system and react with oxidants such as silver nitrate. The reducing effect of ascorbic acid may help to reduce the gold ions and silver ions in the chloroauric acid solution and the silver nitrate solution into gold molecules and silver molecules, and the gold molecules and silver molecules exist in the form of nanoparticles.

[0025] Specifically, the gold acid is the source of gold. During the reaction, the gold ions in the chloroauric acid are reduced under the action of a reducing agent such as ascorbic acid, thereby forming gold-related components in the final product, which may be gold nanoparticles or other gold compound forms, and are indispensable substances for preparing the target product.

[0026] Implementation column data comparison Except that the concentration of the silver nitrate solution used is different from that in Example 1, other conditions in Example 2 are consistent with those in Example 1.

[0027] Table 1

[0028] It can be seen from Table 1 above that as the concentration of the acid-silver solution changes, the particle size of the gold-silver nanoflower particles will also change synchronously.

[0029] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention. The scope of the present invention is defined by the attached claims and their equivalents.

Claims

1. A method for preparing gold and silver nanoflower particles with a core-shell structure, characterized in that: The preparation method comprises the following steps: Step 1: First, prepare polylysine powder, accurately weigh 0.4 g of polylysine powder, select 40 ml of ultrapure water as a solvent, add the weighed polylysine powder into the ultrapure water, and then use an ultrasonic dissolution method to finally obtain a 1.0 wt% polylysine solution for subsequent use; Step 2: Take 4 ml of the previously prepared 1.0 wt% polylysine solution, and then measure 36 ml of ultrapure water, add 4 ml of the 1.0 wt% polylysine solution to 36 ml of ultrapure water, and perform ultrasonic dissolution again. Through this dilution method, a 0.1 wt% polylysine solution is obtained for the next reaction; Step 3, taking out 4 ml from the 0.1wt% polylysine solution, and then preparing 36 ml of ultrapure water, adding 4 ml of the 0.1wt% polylysine solution into 36 ml of ultrapure water, and dissolving by ultrasonication to obtain a 0.01wt% polylysine solution; Step 4, weigh 0.01g of silver nitrate particles, select 10ml of ultrapure water as a solvent, add the weighed silver nitrate particles into the ultrapure water, use ultrasonic dissolution to completely dissolve the silver nitrate in the ultrapure water, obtain a silver nitrate solution with a concentration of 6mmol / L, and store it for subsequent reactions; Step 5, weigh 0.176 g of ascorbic acid powder, take 10 ml of ultrapure water, add the ascorbic acid powder to the ultrapure water, and dissolve it by ultrasound to obtain a 0.1 mol / L ascorbic acid solution, which will react with other reagents in the subsequent reaction; Step 6, weigh 1 g of chloroauric acid trihydrate powder, measure 80 ml of deionized water, add the weighed chloroauric acid trihydrate powder into the deionized water, and perform ultrasonic dissolution operation to obtain a 1 wt% chloroauric acid solution for subsequent reaction process; Step 7, take 50 μl of 0.1wt% polylysine solution, add it to a glass reaction bottle filled with 10 ml of ultrapure water, stir the solution in the reaction bottle at room temperature for 2 min, then add 75 μl of 1wt% chloroauric acid solution, and continue stirring for 2 min to fully mix the polylysine solution and the chloroauric acid solution and undergo a preliminary reaction, then add 30 μl of 6mmol / L silver nitrate solution, and then quickly add 40 μl of 0.1mol / L ascorbic acid solution within 45 s. When adding the ascorbic acid solution, it needs to be completed in a short time, which helps to control the progress of the reaction. At this time, it can be observed that the solution quickly changes from colorless to blue, indicating that the reaction is ongoing and new substances are generated. After continuing the reaction for 10 min, stirring is stopped to obtain the product prepared in this embodiment.

2. The method for preparing gold-silver nanoflower particles with a core-shell structure according to claim 1, characterized in that: The polylysine may play the role of a template or a stabilizer. The polylysine solution is gradually diluted during the preparation process in order to control the stabilizing effect of the polylysine solution. The low concentration of polylysine solution can provide a stable reaction environment for subsequent reactions, which is helpful for the directional progress of the reaction of gold molecules attaching to the surface of silver molecules.

3. The method for preparing gold-silver nanoflower particles with a core-shell structure according to claim 1, characterized in that: The silver nitrate is an oxidant. In the reaction system with ascorbic acid and other substances, the silver molecules in the silver nitrate are precipitated and used as a stabilizing core. At the same time, the silver nitrate can affect the reduction process of the gold ions, so that the separated gold molecules are affected, and the particle size and shape of the gold molecules can be controlled. By changing the amount of silver nitrate, the final particle size and shape of the gold-silver nanoflower particles can be changed.

4. The method for preparing gold-silver nanoflower particles with a core-shell structure according to claim 3, characterized in that: The ascorbic acid is a reducing agent, which can provide electrons in the reaction system and react with oxidants such as silver nitrate. The reducing effect of ascorbic acid may help to reduce the gold ions and silver ions in the chloroauric acid solution and the silver nitrate solution into gold molecules and silver molecules, and the gold molecules and silver molecules exist in the form of nanoparticles.

5. The method for preparing gold-silver nanoflower particles with a core-shell structure according to claim 4, characterized in that: The gold acid is the source of gold. During the reaction, the gold ions in the chloroauric acid are reduced under the action of a reducing agent such as ascorbic acid, thereby forming gold-related components in the final product, which may be gold nanoparticles or other gold compound forms, and are indispensable substances for preparing the target product.

6. An application of the gold-silver nanoflower particles with a core-shell structure as claimed in any one of claims 1 to 5, characterized in that: The gold-silver nanoflower particles are used in the field of biosensing or medical diagnosis.

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