CN114082973B - Ag shell thickness control method of Au @ Ag nano core-shell material and application thereof - Google Patents

Ag shell thickness control method of Au @ Ag nano core-shell material and application thereof Download PDF

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CN114082973B
CN114082973B CN202111231897.5A CN202111231897A CN114082973B CN 114082973 B CN114082973 B CN 114082973B CN 202111231897 A CN202111231897 A CN 202111231897A CN 114082973 B CN114082973 B CN 114082973B
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范文宏
梁***
王祥瑞
王颖
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Beihang University
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Abstract

The Ag shell thickness control method of the Au @ Ag nano core-shell material and the application thereof utilize ascorbic acid to reduce Ag + in silver nitrate solution, and simultaneously adopt a mode of gradual dropping and ammonia water complexing to slow down the reduction rate of Ag +, the amount of added Ag + can be calculated through a relational formula between the silver nitrate solution and the grain diameter of the nano gold core and the grain diameter of the Au @ Ag nano core-shell material, and a series of Au @ Ag NPs with controllable Ag shell thickness are synthesized by controlling the volume of the added silver nitrate solution. The strength of the Au nuclear electron compensation effect is changed by controlling the thickness of the Ag shell, so that the thickness of the Ag shell suitable for being applied to the fields of biomedicine and biological tracking is obtained.

Description

Ag shell thickness control method of Au @ Ag nano core-shell material and application thereof
Technical Field
The invention relates to the field of environmental material research, in particular to an Ag shell thickness control method of an Au @ Ag nano core-shell material and application thereof.
Background
Silver nanoparticles (Ag NPs) have attracted worldwide attention due to their unique optical, catalytic, sensing and antimicrobial properties. The plasma resonance effect of the Ag NPs enables the Ag NPs to have wide application prospects in the fields of biosensing, surface-enhanced Raman scattering spectroscopy, plasma nano-laser technology, solar energy collection and the like. However, since Ag NPs have poor chemical stability and biocompatibility and are easily oxidized, the plasma performance is reduced, and further the release of silver ions (Ag ion, ag +) is promoted, which may cause great biological toxicity. However, because of their excellent antifungal and antibacterial properties, ag NPs are widely used in various commercial products, including mobile phones, toothbrushes, cosmetics, textiles, and the like. With the widespread use of Ag NPs in consumer products, people are increasingly paying more attention to the possible health impact they may have and the potential impact they may have on ecosystem release into the environment. However, the evaluation of the biological fate of the Ag NPs is very challenging, because the biological accumulation and transportation of the Ag NPs in organisms are very complicated, and the oxidative dissolution and the re-reduction processes exist at the same time, so that a unified conclusion cannot be obtained.
With the research, au @ Ag core-shell nano-materials (Au @ Ag nanoparticles, au @ Ag NPs) are found to show more promising plasma properties than the single Ag NPs and Au/Ag nano-structures, which arouses the attention of people on how to improve the safety of the Ag shell. In addition, the Au nuclear labeled Ag NPs can distinguish the particle state Ag from the ion state Ag by using a conventional metal analysis instrument, and meanwhile, compared with external labels such as fluorescent labels and the like, the Au label in the nano material does not change the surface of the Ag NPs, so the Au nuclear labeling technology is a very promising biological tracking technology, but the Au @ Ag NPs can substitute for the Ag NPs for biological tracking, whether the Au nucleus can influence the biological accumulation and toxicity of the Ag NPs or not is lacked in the systematic research. Moreover, from previous research, an electronic compensation phenomenon from Au to Ag is found in Au-Ag nano structures (such as Au-Ag core-shell structures and alloys), which is beneficial to electronic enrichment on the Ag side and prevention of Ag oxidation, and further reduces the release of Ag +, however, under the condition that the particle size of the nano Au core is fixed, the electronic compensation effect is weakened by increasing the thickness of the Ag shell, so that the Au-Ag nano structures are not safe to use in organisms. Because the Ag shell thickness of the Au @ Ag core-shell nano material can not be quantitatively controlled, the influence and influence degree on biological accumulation and biological toxicity can not be effectively evaluated, and the application range of the Au @ Ag core-shell nano material is seriously influenced.
Disclosure of Invention
The invention provides an Ag shell thickness control method of an Au @ Ag nano core-shell material and application thereof. The invention also discloses the evaluation of the relationship between the thickness of different Ag shells in Au @ Ag NPs and the biological accumulation and toxicity.
The technical scheme of the invention is as follows:
a method for controlling the thickness of an Ag shell of an Au @ Ag nano core-shell material is characterized by comprising the following steps:
s1, re-suspending the nano gold cores with known average particle sizes with ultrapure water to obtain a nano gold solution;
s2, mixing the nano-gold solution with ascorbic acid and concentrated ammonia water to obtain a growth mixed solution;
s3, under the stirring condition, keeping out of the sun, and dropwise adding a silver nitrate solution into the growth mixed solution to obtain the Au @ Ag nano core-shell material with the specified particle size, wherein the relation formula between the silver nitrate solution and the particle size of the nano gold core and the particle size of the Au @ Ag nano core-shell material is as follows:
Figure BDA0003316221410000021
wherein the content of the first and second substances,
Figure BDA0003316221410000022
volume of silver nitrate solution, V Au Volume of growth mixture solution, C Au To grow the concentration of nanogold in the mixed solution, rho Ag Is the density of silver atoms, d Au@Ag The average particle diameter of the Au @ Ag nano core-shell material to be obtained, d Au core Is the average grain diameter of the nano gold core,
Figure BDA0003316221410000023
concentration of silver nitrate solution, p Au Is the density of gold atoms.
Preferably, the concentration of the ascorbic acid is 0.1Mol-0.12Mol, and the concentration of the concentrated ammonia water is 5%.
Preferably, the concentration of the silver nitrate solution is 1mMol/L-10mMol/L, and the dropping speed is 0.1mL/min-1mL/min.
Preferably, the Au @ Ag nano core-shell material is a nanosphere with a gold core surface coated with a silver nano shell layer.
Preferably, the preparation steps of the nano gold core are as follows,
s1.1, under the magnetic stirring condition with the rotating speed of 600rpm, adding 0.1Mol of freshly dissolved sodium borohydride into 0.25mMol of mixed solution of chloroauric acid and 0.25mMol of sodium citrate, and continuously stirring for 4 hours to obtain Jin Jingchong solution; wherein the volume ratio of the sodium borohydride to the mixed solution of the chloroauric acid and the sodium citrate is 3;
s1.2, adding the obtained gold seed crystal solution into a growth solution under the magnetic stirring condition with the rotating speed of 600rpm, stirring for 10min, and carrying out centrifugal collection to obtain the nano gold core; wherein the growth solution is a mixed solution of 1.66g/L of polyvinylpyrrolidone, 2.67mMol of potassium iodide, 1.67mMol of ascorbic acid and 1mMol of chloroauric acid; the volume ratio of the Jin Jingchong solution to the growth solution is determined according to the particle size of the nano gold core to be prepared.
The application of the Au @ Ag nano core-shell material in the biological tracking technology research is characterized in that the Au @ Ag nano core-shell material with different Ag shell thicknesses is synthesized according to the Ag shell thickness control method of the Au @ Ag nano core-shell material, and the influence of the different Ag shell thicknesses on the biological tracking technology is researched.
Preferably, the thickness of the Ag shell of the Au @ Ag nano core-shell material used for the biological tracking technology is not less than 20nm.
The application of the Au @ Ag nano core-shell material in biomedical research is characterized in that the Au @ Ag nano core-shell material with different Ag shell thicknesses is synthesized according to the Ag shell thickness control method of the Au @ Ag nano core-shell material, and the influence of the different Ag shell thicknesses on the biological accumulation is researched, and the specific method comprises the following steps: under the room temperature condition, take the Au @ Ag nanometer nucleocapsid material of different shell thickness to dilute to the same mass concentration, add protozoan thermophilic tetrahymena SB210 strain, after the exposure, collect the cell through centrifugal cleaning's mode, detect the condition of ingesting of tetrahymena cell to different Au @ Ag nanometer nucleocapsid materials to do the contrast with the biological ingesting of Ag NPs under the same particle concentration, aassessment Au @ Ag nanometer nucleocapsid material shell thickness and biological accumulation's relation.
An Au @ Ag nano core-shell material is applied to biomedical research, the Au @ Ag nano core-shell material with different Ag shell thicknesses is synthesized according to the Ag shell thickness control method of the Au @ Ag nano core-shell material, and the influence of the different Ag shell thicknesses on biotoxicity is researched, and the specific method comprises the following steps: under the condition of room temperature, the Au @ Ag nano core-shell material with different shell thicknesses is diluted to the same mass concentration, the protozoan tetrahymena thermophile SB210 strain is added, after exposure is finished, the number of the tetrahymena in different exposure solutions is determined by a blood counting method, and is compared with the number of the exposed cells of the Ag NPs with the same particle concentration, and the relation between the thickness of the Au @ Ag nano core-shell material shell and the biological survival rate is evaluated.
An Au @ Ag nano core-shell material is applied to chemical stability research, the Au @ Ag nano core-shell materials with different Ag shell thicknesses are synthesized according to the Ag shell thickness control method of the Au @ Ag nano core-shell material, and the influence of the different Ag shell thicknesses on the chemical stability research is researched; the specific method comprises the following steps: under the condition of room temperature, diluting the nano core-shell materials with different shell thicknesses to the same mass concentration, oscillating at a constant speed, sampling at different time intervals, measuring the concentration of dissolved Ag + in the solution by using a fluorescent probe, comparing the concentration with the dissolution of Ag NPs under the same particle concentration, and evaluating the relation between the thickness of the Au @ Ag NPs shell and the chemical stability.
Compared with the prior art, the invention has the advantages that: the Ag shell thickness control method of the Au @ Ag nano core-shell material and the application thereof utilize ascorbic acid to reduce Ag + in silver nitrate solution, simultaneously adopt a mode of gradually dripping and complexing with ammonia water to slow down the reduction rate of Ag +, the amount of the added Ag + can be calculated by a relational formula between the grain diameter of the silver nitrate solution and the nano gold core and the grain diameter of the Au @ Ag nano core-shell material, and a series of Au @ Ag NPs with controllable Ag shell thickness are synthesized by controlling the volume of the added silver nitrate solution. The strength of the Au nuclear electron compensation effect is changed by controlling the thickness of the Ag shell, so that the thickness of the Ag shell suitable for being applied to the fields of biomedicine and biological tracking is obtained. If good chemical stability and biocompatibility are pursued, thinning of the Ag shell can be regulated, and thickening of the Ag shell can be regulated if biological tracking of AgNPs is simulated and researched. And has wide application value for other fields.
Drawings
FIG. 1 is a transmission electron microscope image of Au @ Ag NPs prepared by the Ag shell thickness control method of Au @ Ag nano core-shell material of the invention;
FIG. 2 is a morphology of Au @ Ag NPs prepared by the Ag shell thickness control method of Au @ Ag nano core-shell material of the invention.
FIG. 3 is a comparison graph of chemical stability evaluation in environment of Au @ Ag NPs of different Ag shell thicknesses prepared by the Ag shell thickness control method of Au @ Ag nano core-shell material of the present invention.
FIG. 4 is a comparison graph of the effects of Au @ Ag NPs with different Ag shell thicknesses and Ag NPs with the same outer diameter on biological uptake, which are prepared by the Ag shell thickness control method of the Au @ Ag nano core-shell material.
FIG. 5 is a comparison graph of the effect of Au @ Ag NPs with different Ag shell thicknesses and Ag NPs with the same outer diameter on the biological toxicity, which are prepared by the Ag shell thickness control method of Au @ Ag nano core-shell materials of the invention.
Detailed Description
In order to facilitate understanding of the present invention, the present invention will be described in more detail below with reference to specific examples and comparative examples.
Example 1
A method for controlling the thickness of an Ag shell of an Au @ Ag nano core-shell material comprises the following steps:
s1, taking 3mg of nano gold core with known average particle size, re-suspending to 15mL with ultrapure water, and performing ultrasonic treatment for 20min under the power of 250W by using an ultrasonic cleaner to obtain a nano gold solution;
wherein the preparation steps of the nano gold core with known average particle size are as follows:
s1.1, under the magnetic stirring condition with the rotating speed of 600rpm, adding 0.1Mol of freshly dissolved sodium borohydride into 0.25mMol of mixed solution of chloroauric acid and 0.25mMol of sodium citrate, and continuously stirring for 4 hours to obtain Jin Jingchong solution; wherein the volume ratio of the sodium borohydride to the mixed solution of the chloroauric acid and the sodium citrate is 3;
s1.2, when preparing a nano gold core with the particle size of about 20nm, adding the obtained gold seed crystal solution into a growth solution at a volume ratio of 1; wherein the growth solution is a mixed solution of 1.66g/L of polyvinyl pyrrolidone, 2.67mMol of potassium iodide, 1.67mMol of ascorbic acid and 1mMol of chloroauric acid.
Detection shows that the average grain diameter of the nano gold cores prepared in the steps S1.1-S1.2 is 20.7nm.
S2, placing the nano-gold solution into a conical flask, and mixing the nano-gold solution with 1.5mL of ascorbic acid, 3mL of concentrated ammonia water and 10.5mL of ultrapure water to obtain a growth mixed solution; wherein the concentration of the ascorbic acid is 0.1Mol, and the concentration of the concentrated ammonia water is 5%; the concentration of the nano-gold in the growth mixed solution is 100mg/L;
s3, under the magnetic stirring condition of the rotation speed of 600rpm, keeping out of the sun, dropwise adding a quantitative silver nitrate solution with the concentration of 5mMol/L into the growth mixed solution at the dropwise adding speed of 0.5mL/min to obtain the Au @ Ag nano core-shell material with the specified particle size, wherein the relationship among the quantitative silver nitrate solution, the particle size of the nano gold core and the particle size of the Au @ Ag nano core-shell material is as follows:
Figure BDA0003316221410000041
wherein the content of the first and second substances,
Figure BDA0003316221410000042
volume of silver nitrate solution, V Au For the life of a living beingVolume of long mixed solution, C Au For growing the concentration of nanogold in the mixed solution, rho Ag Is the density of silver atoms, d Au@Ag The particle size of the Au @ Ag nano core-shell material to be obtained, d Au core Is the grain diameter of the nano-gold core,
Figure BDA0003316221410000043
is the concentration of silver ions in the silver nitrate solution, p Au Is the density of gold atoms.
In S3, the volume V of the growth mixed solution Au 30mL, concentration C of nanogold in growth mixed solution Au The silver ion concentration in the silver nitrate solution is 100mg/L and the concentration of the silver nitrate solution is 5mMol/L
Figure BDA0003316221410000051
0.54g/L, when the particle size of the Au @ Ag nano core-shell material is 25nm, the volume of silver nitrate solution which should be added theoretically
Figure BDA0003316221410000052
Calculated to be 2.31mL. When the particle size of the Au @ Ag nano core-shell material is to be 40nm, the volume of silver nitrate solution should be added theoretically
Figure BDA0003316221410000053
Calculated to be 18.8mL. When the particle size of the Au @ Ag nano core-shell material is 60nm, the volume of silver nitrate solution should be added theoretically
Figure BDA0003316221410000054
Calculated to be 70.7mL. When the particle size of the Au @ Ag nano core-shell material is 80nm, the volume of silver nitrate solution which should be added theoretically
Figure BDA0003316221410000055
Calculated to be 17108mL.
When the total volume of silver nitrate of 2.31mL,18.8mL,70.7mL,171.8mL was actually added, the rotational speed of the synthesized Au @ Ag NPs after the reaction was 6000-9000G, and the reaction mixture was centrifugedAfter centrifugal collection for 10min, centrifugally cleaning the obtained Au @ Ag nano core-shell material twice by using ultrapure water, after each centrifugal process, carrying out resuspension, carrying out ultrasonic cleaning for 20min under the power of 250W by using an ultrasonic cleaner, and scanning by using a transmission electron microscope to obtain transmission electron microscope images of four Au @ Ag nano core-shell materials (Au @ Ag NPs), which are shown in a figure 1 (a); scanning transmission electron microscope scanning is carried out to obtain a scanning transmission electron microscope image of the four Au @ Ag nano core-shell materials, which is shown in figure 1 (b); energy-dispersive X-ray images of the four Au @ Ag NPs were obtained using X-ray energy spectral analysis, see FIG. 1 (c). The results of transmission electron microscopy images show that core-shell nanostructures have been achieved. The results of the scanning transmission electron microscopy images clearly show that a very bright central region is surrounded by a less bright peripheral region, indicating that the Au core is covered by Ag cores of different thicknesses. The results in FIG. 1c show that Au (dark color) and Ag (light color) are present in Au @ Ag NPs, au is confined in the core region of the particle, and Ag surrounds the Au core and the Ag shell thickness is different. As can be seen from FIG. 2, the particle sizes of Au nucleus and Au @ Ag NPs were 20.7nm, 25.4. + -. 0.3nm, 47.2. + -. 1.4nm, 64.3. + -. 0.4nm, and 76.6. + -. 1.4nm, respectively, and the nanoparticles were uniformly dispersed and the particle size was uniform without agglomeration. And the Ag shell thicknesses of Au @ Ag NPs are respectively 2.5nm,13.3nm,21.8nm and 28.0nm. The calculation method of the thickness of the Ag shell of Au @ Ag NPs is (d) Au@Ag -d Aucore )÷2。
A series of Au @ Ag NPs (namely Au @ Ag NPs with different Ag shell thicknesses) with different particle sizes prepared by the method utilize ascorbic acid to reduce Ag +, and simultaneously adopt a mode of gradually dropping and complexing with ammonia water to slow down the reduction rate of Ag +. The particle size of the finally synthesized Au @ Ag NPs is related to the amount of Ag + added, and the amount of Ag + added can be calculated through a relational formula between the silver nitrate solution and the particle size of the nano gold core and the particle size of the Au @ Ag nano core-shell material.
Example 2
The application of the Au @ Ag nano core-shell material in the biological tracking technology research is characterized in that the Au @ Ag nano core-shell material with different Ag shell thicknesses is synthesized according to the Ag shell thickness control method of the Au @ Ag nano core-shell material, and the influence of the different Ag shell thicknesses on the biological tracking technology is researched. The Ag shell thickness of the Au @ Ag nano core-shell material for the biological tracking technology is not less than 20nm.
Example 3
An Au @ Ag nano core-shell material is applied to chemical stability research, the Au @ Ag nano core-shell materials with different Ag shell thicknesses are synthesized by using the Ag shell thickness control method of the Au @ Ag nano core-shell material, and the influence of the different Ag shell thicknesses on the chemical stability research is researched; the specific method comprises the following steps: under the condition of room temperature, diluting Au @ Ag nano core-shell materials with different shell thicknesses to 5mg/L (calculated by Ag), adding a protozoan Thermopsis mollis SB210 strain, oscillating the solution at a constant speed, rotating at the speed of 120rpm, sampling at 0,1,2,5,7,18,28,48 and 67h after exposure is finished, collecting cells in a centrifugal cleaning mode, adding an Ag + determination fluorescent probe TEZ-TPE-1, enabling the final probe concentration to be 30 mu M, and detecting the ingestion condition of the Tetrahymena cells on different Au @ Ag nano core-shell materials. For comparison, ag NPs of the same size as the Au @ Ag NPs nanoparticles were exposed simultaneously, with conditions consistent with those before.
FIG. 3 is a graph of chemical stability evaluation of Au @ Ag NPs in water environment at different Ag shell thicknesses. The result shows that the dissolution amount of the Au @ Ag NPs is remarkably lower than that of the Ag NPs with the same grain size, but the dissolution difference is gradually reduced along with the increase of the thickness of the Ag shell, and the remarkable difference between the dissolution amount of the Ag NPs and that of the Au @ Ag NPs with the same grain size is noted even when the thickness of the shell is increased to 28nm, which shows that the Au core can reduce the dissolution behavior of the Ag NPs in the water environment. Compared with Ag NPs, the Au @ Ag NPs have stronger chemical stability, and the Au @ Ag NPs are also suggested to have lower biotoxicity.
Example 4
The application of the Au @ Ag nano core-shell material in biomedical research is characterized in that the Au @ Ag nano core-shell material with different Ag shell thicknesses is synthesized by using the Ag shell thickness control method of the Au @ Ag nano core-shell material, and the influence of the different Ag shell thicknesses on the biological accumulation is researched, and the specific method comprises the following steps: at room temperature of 25 ℃, au @ Ag NPs with different shell thicknesses are diluted to 10mg/L (calculated by Ag), protozoan thermophilic tetrahymena SB210 strains in logarithmic growth phase are added, the strains are mixed according to the volume ratio of 1:1, the final concentration of the Au @ Ag NPs is 5mg/L, the concentration of the tetrahymena is 50 ten thousand/mL, the biological exposure liquid is oscillated at constant speed and the rotating speed is 120rpm, the lightproof exposure is carried out for 6h, after the exposure is finished, the sample is centrifuged at the rotating speed of 600G for 5min, the precipitate is cleaned for 2 times, and the content of Ag accumulated by the cells is measured by using an inductively coupled plasma mass spectrometer. For comparison, ag NPs of the same size as the Au @ Ag NPs nanoparticles were exposed simultaneously, with conditions consistent with those before.
FIG. 4 is a graph comparing the effect of Au @ Ag NPs of different Ag shell thicknesses and Ag NPs of the same outer diameter on bioabsorption. The result shows that the biological accumulation amounts of Au @ Ag NPs and Ag NPs with the same particle size are consistent, and the Au nucleus has no obvious influence on the uptake of the nano material into tetrahymena cells. The result proves that Au @ Ag NPs can replace Ag NPs for biological tracking and is an ideal biomarker means.
Example 5
The application of the Au @ Ag nano core-shell material in biomedical research is characterized in that the Au @ Ag nano core-shell material with different Ag shell thicknesses is synthesized by using the Ag shell thickness control method of the Au @ Ag nano core-shell material, and the influence of the different Ag shell thicknesses on the biological accumulation is researched, and the specific method comprises the following steps: at the condition of room temperature of 25 ℃, taking Au @ Ag NPs with different shell thicknesses to dilute to 40mg/L (calculated by Ag), adding protozoan thermophilic tetrahymena SB210 strain in logarithmic growth phase, mixing according to the volume ratio of 1:1, wherein the final concentration of the Au @ Ag NPs is 20mg/L, the concentration of the tetrahymena is 50 ten thousand/mL, the biological exposure liquid oscillates at constant speed, the rotating speed is 120rpm, and the biological sample is exposed in dark for 6h, and after the exposure is finished, the biological sample counts the survival cells by a blood cell counting method. For comparison, ag NPs of the same size as the Au @ Ag NPs nanoparticles were exposed simultaneously, with conditions consistent with those before.
FIG. 5 is a graph comparing the effect of Au @ Ag NPs of different Ag shell thicknesses and Ag NPs of the same outer diameter on biotoxicity. The results indicate that the toxicity of Au @ Ag NPs to cells is significantly lower than that of Ag NPs with the same particle size, and the biological toxicity of Au @ Ag NPs and the toxic effect of Ag NPs gradually tend to be consistent with the increase of the shell thickness, which is consistent with the chemical stability results of FIG. 3. The result proves the huge application scene of Au @ Ag NPs in the fields of biomedicine and biological tracking.
It should be noted that the above-described embodiments may enable those skilled in the art to more fully understand the present invention, but do not limit the present invention in any way. Therefore, although the present invention has been described in detail with reference to the drawings and examples, it will be understood by those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention.

Claims (9)

1. A method for controlling the thickness of an Ag shell of an Au @ Ag nano core-shell material is characterized by comprising the following steps:
s1, resuspending the nanogold core with the known average particle size with ultrapure water to obtain a nanogold solution;
s2, mixing the nano-gold solution with ascorbic acid and concentrated ammonia water to obtain a growth mixed solution;
s3, under the stirring condition, keeping out of the sun, and dropwise adding a silver nitrate solution into the growth mixed solution to obtain the Au @ Ag nano core-shell material with the specified particle size, wherein the relationship between the silver nitrate solution and the particle size of the nano gold core and the particle size of the Au @ Ag nano core-shell material is as follows:
Figure FDA0003959874840000011
wherein the content of the first and second substances,
Figure FDA0003959874840000012
volume of silver nitrate solution, V Au Volume of growth mixture solution, C Au For growing the concentration of nanogold in the mixed solution, rho Ag Is the density of silver atoms, d Au@Ag The average particle diameter of the Au @ Ag nano core-shell material to be obtained, d Au core Is the average grain diameter of the nano gold core,
Figure FDA0003959874840000013
concentration of silver nitrate solution, p Au Is the density of gold atoms.
2. The method for controlling the thickness of the Ag shell of the Au @ Ag nano core-shell material according to claim 1, wherein the concentration of the ascorbic acid is 0.1Mol-0.12Mol, and the concentration of the concentrated ammonia water is 5%.
3. The method for controlling the thickness of the Ag shell of the Au @ Ag nano core-shell material according to claim 1, wherein the concentration of the silver nitrate solution is 1mMol/L to 10mMol/L, and the dropping speed is 0.1mL/min to 1mL/min.
4. The method for controlling the thickness of the Ag shell of the Au @ Ag nano core-shell material according to claim 1, wherein the Au @ Ag nano core-shell material is a nanosphere with a gold core surface coated with a silver nano shell layer.
5. The Ag shell thickness control method of Au @ Ag nano core-shell material according to claim 1, characterized in that the preparation steps of the nano gold core are as follows,
s1.1, under the magnetic stirring condition with the rotating speed of 600rpm, adding 0.1Mol of freshly dissolved sodium borohydride into 0.25mMol of mixed solution of chloroauric acid and 0.25mMol of sodium citrate, and continuously stirring for 4 hours to obtain Jin Jingchong solution; wherein the volume ratio of the sodium borohydride to the mixed solution of the chloroauric acid and the sodium citrate is 3:100;
s1.2, adding the obtained gold seed crystal solution into a growth solution under the magnetic stirring condition with the rotating speed of 600rpm, stirring for 10min, and carrying out centrifugal collection to obtain the nano gold core; wherein the growth solution is a mixed solution of 1.66g/L of polyvinyl pyrrolidone, 2.67mMol of potassium iodide, 1.67mMol of ascorbic acid and 1mMol of chloroauric acid; the volume ratio of the Jin Jingchong solution to the growth solution is determined according to the particle size of the nano gold core to be prepared.
6. An application of Au @ Ag nano core-shell material in biological tracking technology research is characterized in that Au @ Ag nano core-shell materials with different Ag shell thicknesses are synthesized according to the Ag shell thickness control method of the Au @ Ag nano core-shell material in any one of claims 1 to 5, and the influence of the different Ag shell thicknesses on the biological tracking technology is researched;
the Ag shell thickness of the Au @ Ag nano core-shell material for the biological tracking technology is not less than 20nm.
7. An application of Au @ Ag nano core-shell material in biomedical research is characterized in that Au @ Ag nano core-shell materials with different Ag shell thicknesses are synthesized according to the Ag shell thickness control method of Au @ Ag nano core-shell material in any one of claims 1 to 5, the influence of different Ag shell thicknesses on bioaccumulation is researched, and the specific method comprises the following steps: under the room temperature condition, take the Au @ Ag nanometer nucleocapsid material of different shell thickness to dilute to the same mass concentration, add protozoan thermophilic tetrahymena SB210 strain, after the exposure, collect the cell through centrifugal cleaning's mode, detect the condition of ingesting of tetrahymena cell to different Au @ Ag nanometer nucleocapsid materials to do the contrast with the biological ingesting of Ag NPs under the same particle concentration, aassessment Au @ Ag nanometer nucleocapsid material shell thickness and biological accumulation's relation.
8. An application of Au @ Ag nano core-shell material in biomedical research is characterized in that Au @ Ag nano core-shell materials with different Ag shell thicknesses are synthesized according to the Ag shell thickness control method of Au @ Ag nano core-shell material in any one of claims 1 to 5, and the influence of different Ag shell thicknesses on biotoxicity is researched, and the specific method comprises the following steps: under the condition of room temperature, the Au @ Ag nano core-shell material with different shell thicknesses is diluted to the same mass concentration, the protozoan tetrahymena thermophile SB210 strain is added, after exposure is finished, the number of the tetrahymena in different exposure solutions is determined by a blood counting method, and is compared with the number of the exposed cells of the Ag NPs with the same particle concentration, and the relation between the thickness of the Au @ Ag nano core-shell material shell and the biological survival rate is evaluated.
9. An application of Au @ Ag nano core-shell material in chemical stability research is characterized in that Au @ Ag nano core-shell materials with different Ag shell thicknesses are synthesized according to the Ag shell thickness control method of Au @ Ag nano core-shell material in any one of claims 1 to 5, and the influence of different Ag shell thicknesses on the chemical stability research is researched; the specific method comprises the following steps: under the condition of room temperature, diluting the nano core-shell materials with different shell thicknesses to the same mass concentration, oscillating at a constant speed, sampling at different time intervals, measuring the concentration of dissolved Ag + in a solution by using a fluorescent probe, comparing the concentration with the dissolution of Ag NPs with the same particle concentration, and evaluating the relation between the shell thickness of Au @ Ag NPs and the chemical stability.
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