CN113369475A - Preparation method and application of carbon-based thin-film gold nanoparticles with adjustable film thickness - Google Patents
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Abstract
A preparation method and application of carbon-based thin-film gold nanoparticles with adjustable film thickness relate to a preparation method of gold/carbon-based nano-film core-shell structure nanoparticles. The invention aims to solve the problem that the existing coating material is difficult to form a film at a low nanometer or even sub-nanometer scale and cannot construct a multi-element composite material. The method comprises the following steps: adding hyaluronic acid into a gold nano solution, and stirring at room temperature to obtain a reaction solution; secondly, transferring the reaction liquid to a hydrothermal reaction kettle for hydrothermal reaction; and thirdly, centrifuging, and filtering by adopting a 0.22-micron water system micro-pore filtering membrane to obtain the carbon-based thin-film gold nanoparticles with adjustable membrane thickness. Carbon-based filmed gold nanoparticles with adjustable membrane thickness can be used to respond to tumor microenvironment. The invention can obtain the carbon-based thin-film gold nanoparticle composite material with adjustable film thickness.
Description
Technical Field
The invention relates to a preparation method of gold/carbon-based nano film core-shell structure nano particles.
Background
The film coating technology plays an important role in the construction of composite materials and the protection of core nano materials. In the surface enhanced Raman scattering spectroscopy technology, the gap enhanced Raman signal element is excellent in obtaining remarkable electromagnetic field enhancement and extremely strong Raman signals. Maxwell's equations predict that the electromagnetic field will increase as the distance between the metal nanostructures decreases and be confined to the ultra-fine nanogap. In order to obtain a high concentration of strong electric field, a lot of effort has been made in the preparation of plasma structures, revealing that gaps or films smaller than 10nm are the key to obtaining high enhancement factor plasma structures. Besides the function of a nanometer ruler, the nanometer film material is also an important investigation factor for further constructing high-quality Raman signal elements. In addition, the excellent performance of the nano-film itself can provide more possibilities for the construction of multifunctional composite nano-materials. Currently, the adjustable membranes are mainly silicon dioxide membranes and polydopamine membranes. These two types of materials have good tunability at high nanoscale, but are difficult to form into films at low nanometer (less than 3nm) and even sub-nanometer scale. The carbon-based material, as an economical and environment-friendly material widely studied in various fields in recent years, exhibits excellent optical, electrical and catalytic properties. However, the research on carbon-based materials as tunable nano-films is very rare, and a few of reports in the literature currently show that films obtained by synthetic methods are all of a single size and cannot ensure the uniformity of film formation, and most of the films cover a plurality of randomly arranged particles. Finally, based on the research of the synthesis method of the carbon-based nano film with controllable film thickness in the range of low nanometer and even sub-nanometer scale, the method can provide important theoretical support for the construction of high-efficiency film type gap enhancement models and multifunctional diagnosis models.
Disclosure of Invention
The invention aims to solve the problems that the existing coating material is difficult to form a film at low nanometer and even sub-nanometer scale and cannot construct a multi-element composite material, and provides a preparation method and application of carbon-based film-formed gold nanoparticles with adjustable film thickness.
A preparation method of carbon-based thin-film gold nanoparticles with adjustable film thickness comprises the following steps:
adding hyaluronic acid into a gold nano solution, and stirring at room temperature to obtain a reaction solution;
secondly, transferring the reaction liquid into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 150-200 ℃, and cooling to room temperature to obtain a reaction product;
III,
Firstly, centrifuging a reaction product, and removing supernatant to obtain a precipitate product (carbon-based thin-film gold nanoparticles-AuNPs @ CF); dispersing the precipitated material into distilled water;
and secondly, repeating the third step, and filtering by adopting a 0.22-micron water system microporous filtering membrane to obtain the carbon-based thin film gold nanoparticles with adjustable membrane thickness.
A carbon-based filmed gold nanoparticle with adjustable membrane thickness is used for responding to a tumor microenvironment.
The principle of the invention is as follows:
the core-shell structure nano material is prepared by taking gold nanoparticles (AuNPs) as an inner core and a carbon-based nano film (CF) as an outer shell, the effective regulation and control of the thickness of the carbon-based film coating the gold nanoparticles are realized by regulating and controlling the time and the temperature of hydrothermal reaction and the concentration of reaction liquid, and the thickness of the carbon-based filmed gold nanoparticles can be regulated within 1.39-22.11 nm; the carbon-based thin film gold nanoparticles (AuNPs @ CF) with adjustable film thickness prepared by the invention can be loaded with 3,3',5,5' -Tetramethylbenzidine (TMB) to form an AuNPs @ CF-TMB composite system, wherein the existence of the CF film provides a loading substrate and simultaneously endows the system with the capability of imitating peroxidase, and the carbon-based thin film gold nanoparticles (AuNPs @ CF) have the capability of responding to tumor microenvironment (low pH and high H)2O2Environment) and exhibits a high-contrast near-infrared two-zone photoacoustic imaging effect;
secondly, the LSPR spectrum of the carbon-based thin-film gold nanoparticles with adjustable film thickness prepared by the method has adjustability and is positively correlated with the film thickness.
The invention can obtain the carbon-based thin-film gold nano-particle with adjustable film thickness.
Drawings
FIG. 1 is a transmission electron micrograph of carbon-based thin-film gold nanoparticles prepared in examples 1 to 6, wherein (a) is example 1, (b) is example 2, (c) is example 3, (d) is example 4, (e) is example 5, and (f) is example 6;
FIG. 2 is the SPR peaks of carbon-based thin-film gold nanoparticles prepared in examples 7-13, wherein 25 ℃ is example 7, 150 ℃ is example 8, 160 ℃ is example 9, 170 ℃ is example 10, 180 ℃ is example 11, 190 ℃ is example 12, and 200 ℃ is example 13;
FIG. 3 is the SPR peaks of carbon-based thin-film gold nanoparticles prepared in examples 14-19, wherein 0 is example 14, 5 is example 15, 10 is example 16, 15 is example 17, 20 is example 18, and 30 is example 19;
FIG. 4 is a TEM image of carbon-based thin-film gold nanoparticles with adjustable film thickness prepared in example 18;
FIG. 5 is an electron binding energy spectrum of carbon-based thin-film gold nanoparticles with adjustable film thickness prepared in example 18;
FIG. 6 is a graph of the UV absorption curves for AuNPs @ CF-TMB supported systems at pH 5.0, 5.5, 6.0, 6.5, 7.0, and 7.5;
FIG. 7 is a photo-acoustic plot of AuNPs @ CF-TMB supported system at different concentrations of hydrogen peroxide at pH 5.0.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
The first embodiment is as follows: the preparation method of the carbon-based thin-film gold nanoparticles with adjustable film thickness is specifically completed according to the following steps:
adding hyaluronic acid into a gold nano solution, and stirring at room temperature to obtain a reaction solution;
secondly, transferring the reaction liquid into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 150-200 ℃, and cooling to room temperature to obtain a reaction product;
III,
Firstly, centrifuging a reaction product, and removing supernatant to obtain a precipitate product (carbon-based thin-film gold nanoparticles-AuNPs @ CF); dispersing the precipitated material into distilled water;
and secondly, repeating the third step, and filtering by adopting a 0.22-micron water system microporous filtering membrane to obtain the carbon-based thin film gold nanoparticles with adjustable membrane thickness.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the ratio of the mass of the hyaluronic acid to the volume of the gold nanometer solution in the step one is (10 mg-30 mg):20 mL. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the concentration of the gold nano solution in the step one is 0.32 mg/mL-0.33 mg/mL; the grain diameter of gold in the gold nanometer solution in the step one is 18.3 nm-21.1 nm. The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: the stirring speed in the step one is 1200 r/min-1800 r/min, and the stirring time is 0.5 h-1 h. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the time of the hydrothermal reaction in the second step is 2-12 h. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: and in the second step, transferring the reaction solution into a hydrothermal reaction kettle, and then carrying out hydrothermal reaction at 160-190 ℃. The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: and in the second step, the reaction solution is transferred into a hydrothermal reaction kettle, and then hydrothermal reaction is carried out at 170-180 ℃. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the centrifugation speed is 7000r/min to 8000r/min, and the centrifugation time is 10min to 20 min; the volume ratio of the mass of the precipitate to the distilled water in the third step (0.40 mg-0.60 mg) is 1 mL. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: in the third step, the times of repeating the third step are 3 to 5; and step three, the thickness of the carbon-based thin-film gold nanoparticles with adjustable film thickness is 1.39-22.11 nm. The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the embodiment is that the carbon-based thin-film gold nanoparticles with adjustable membrane thickness are used for responding to a tumor microenvironment.
The present invention will be described in detail below with reference to the accompanying drawings and examples.
Example 1: the preparation method of the carbon-based thin-film gold nanoparticles with adjustable film thickness is specifically completed according to the following steps:
firstly, adding 20mg of hyaluronic acid into 20mL of gold nano solution, and stirring for 0.5h at the stirring speed of 1500r/min at room temperature to obtain a reaction solution;
the concentration of the gold nano solution in the step one is 0.325mg/mL-1；
The grain diameter of gold in the gold nanometer solution in the step one is 18.3 nm-21.1 nm;
secondly, transferring the reaction liquid into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 2 hours at the temperature of 150 ℃, and cooling to room temperature to obtain a reaction product;
III,
Firstly, centrifuging a reaction product, and removing supernatant to obtain a precipitate product (carbon-based thin-film gold nanoparticles-AuNPs @ CF); dispersing the precipitated material into distilled water;
the centrifugation speed in the third step is 8000r/min, and the centrifugation time is 15 min;
the volume ratio of the mass of the precipitate to the distilled water in the third step is 0.5mg:1 mL;
and secondly, repeating the third step, and then filtering by adopting a 0.22-micron water system microporous filtering membrane to obtain the carbon-based thin film gold nanoparticles (AuNPs @ CF) with adjustable membrane thickness.
The thickness of the carbon-based thin-film gold nanoparticles prepared in example 1 was 1.39 nm.
Example 2: the present embodiment is different from embodiment 1 in that: and in the second step, transferring the reaction solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 2h, and cooling to room temperature to obtain a reaction product. The other steps and parameters were the same as in example 1.
The thickness of the carbon-based thin-film gold nanoparticles prepared in example 2 was 3.15 nm.
Example 3: the present embodiment is different from embodiment 1 in that: and in the second step, transferring the reaction solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 3 hours at the temperature of 170 ℃, and cooling to room temperature to obtain a reaction product. The other steps and parameters were the same as in example 1.
The thickness of the carbon-based thin-film gold nanoparticles prepared in example 3 was 4.5 nm.
Example 4: the present embodiment is different from embodiment 1 in that: and in the second step, transferring the reaction solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 5 hours at 180 ℃, and cooling to room temperature to obtain a reaction product. The other steps and parameters were the same as in example 1.
The thickness of the carbon-based thin-film gold nanoparticles prepared in example 4 was 6.59 nm.
Example 5: the present embodiment is different from embodiment 1 in that: and in the second step, transferring the reaction solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 10 hours at 190 ℃, and cooling to room temperature to obtain a reaction product. The other steps and parameters were the same as in example 1.
The thickness of the carbon-based thin-film gold nanoparticles prepared in example 5 was 13.45 nm.
Example 6: the present embodiment is different from embodiment 1 in that: and in the second step, transferring the reaction solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 10 hours at the temperature of 200 ℃, and cooling to room temperature to obtain a reaction product. The other steps and parameters were the same as in example 1.
The thickness of the carbon-based thin-film gold nanoparticles prepared in example 6 was 22.11 nm.
FIG. 1 is a transmission electron micrograph of carbon-based thin-film gold nanoparticles prepared in examples 1 to 6, wherein (a) is example 1, (b) is example 2, (c) is example 3, (d) is example 4, (e) is example 5, and (f) is example 6;
example 7: this example is a method for preparing AuNPs-HA, specifically comprising the following steps: adding 20mg of hyaluronic acid into 20mL of gold nano solution, and stirring at the stirring speed of 1500r/min for 0.5h at 25 ℃ to obtain a reaction solution; the concentration of the gold nano solution is 0.325mg/mL-1(ii) a The grain size of gold in the gold nanometer solution is 18.3 nm-21.1 nm, and AuNPs-HA is obtained.
Example 8: the present embodiment is different from embodiment 1 in that: and in the second step, transferring the reaction solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 10 hours at the temperature of 150 ℃, and cooling to room temperature to obtain a reaction product. The other steps and parameters were the same as in example 1.
Example 9: the present embodiment is different from embodiment 1 in that: and in the second step, transferring the reaction solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 10 hours at 160 ℃, and cooling to room temperature to obtain a reaction product. The other steps and parameters were the same as in example 1.
Example 10: the present embodiment is different from embodiment 1 in that: and in the second step, transferring the reaction solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 10 hours at the temperature of 170 ℃, and cooling to room temperature to obtain a reaction product. The other steps and parameters were the same as in example 1.
Example 11: the present embodiment is different from embodiment 1 in that: and in the second step, transferring the reaction solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 10 hours at 180 ℃, and cooling to room temperature to obtain a reaction product. The other steps and parameters were the same as in example 1.
Example 12: the present embodiment is different from embodiment 1 in that: and in the second step, transferring the reaction solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 10 hours at 190 ℃, and cooling to room temperature to obtain a reaction product. The other steps and parameters were the same as in example 1.
Example 13: the present embodiment is different from embodiment 1 in that: and in the second step, transferring the reaction solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 10 hours at the temperature of 200 ℃, and cooling to room temperature to obtain a reaction product. The other steps and parameters were the same as in example 1.
FIG. 2 is the SPR peaks of carbon-based thin-film gold nanoparticles prepared in examples 7-13, wherein 25 ℃ is example 7, 150 ℃ is example 8, 160 ℃ is example 9, 170 ℃ is example 10, 180 ℃ is example 11, 190 ℃ is example 12, and 200 ℃ is example 13;
as can be seen from FIG. 2, the SPR peak of AuNPs-HA prepared in example 7 blank comparison at room temperature is 521nm, and the SPR peaks of the carbon-based thin-film gold nanoparticles (AuNPs @ CF) with adjustable film thickness prepared in examples 8 to 13 are 535nm, 537nm, 542nm, 543nm, 545nm and 548nm, respectively.
Example 14: the preparation method of the carbon-based thin-film gold nanoparticles with adjustable film thickness is specifically completed according to the following steps:
firstly, adding 0mg of hyaluronic acid into 20mL of gold nano solution, and stirring for 0.5h at the stirring speed of 1500r/min at room temperature to obtain a reaction solution;
the concentration of the gold nano solution in the step one is 0.325mg/mL-1；
The grain diameter of gold in the gold nanometer solution in the step one is 18.3 nm-21.1 nm;
secondly, transferring the reaction liquid into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 10 hours at the temperature of 150 ℃, and cooling to room temperature to obtain a reaction product;
III,
Firstly, centrifuging a reaction product, and removing supernatant to obtain a precipitate product (carbon-based thin-film gold nanoparticles-AuNPs @ CF); dispersing the precipitated material into distilled water;
the centrifugation speed in the third step is 8000r/min, and the centrifugation time is 15 min;
the volume ratio of the mass of the precipitate to the distilled water in the third step is 0.5mg:1 mL;
and secondly, repeating the third step, and then filtering by adopting a 0.22-micron water system microporous filtering membrane to obtain the carbon-based thin film gold nanoparticles (AuNPs @ CF) with adjustable membrane thickness.
Example 15: the present embodiment is different from embodiment 1 in that: in step one, 5mg of hyaluronic acid was added to 20mL of gold nanoparticle solution. The other steps and parameters were the same as in example 1.
Example 16: the present embodiment is different from embodiment 1 in that: in step one, 10mg of hyaluronic acid was added to 20mL of gold nanoparticle solution. The other steps and parameters were the same as in example 1.
Example 17: the present embodiment is different from embodiment 1 in that: in step one, 15mg of hyaluronic acid was added to 20mL of gold nanoparticle solution. The other steps and parameters were the same as in example 1.
Example 18: the present embodiment is different from embodiment 1 in that: in step one, 20mg of hyaluronic acid was added to 20mL of gold nanoparticle solution. The other steps and parameters were the same as in example 1.
Example 19: the present embodiment is different from embodiment 1 in that: in step one, 30mg of hyaluronic acid was added to 20mL of gold nanoparticle solution. The other steps and parameters were the same as in example 1.
FIG. 3 is the SPR peaks of carbon-based thin-film gold nanoparticles prepared in examples 14-19, wherein 0 is example 14, 5 is example 15, 10 is example 16, 15 is example 17, 20 is example 18, and 30 is example 19;
as can be seen from FIG. 3, the film thickness-adjustable carbon-based thin-film gold nanoparticles (AuNPs @ CF) prepared in examples 14 to 19 have peak positions of 521.0nm, 528.0nm, 534.0nm, 540.0nm, 547.0nm and 552.5nm from left to right.
FIG. 4 is a TEM image of carbon-based thin-film gold nanoparticles with adjustable film thickness prepared in example 18;
as can be seen from FIG. 4, the particle size of the carbon-based thin-film gold nanoparticles with adjustable film thickness prepared in example 18 was about 11 nm.
FIG. 5 is an electron binding energy spectrum of carbon-based thin-film gold nanoparticles with adjustable film thickness prepared in example 18;
as can be seen from fig. 5, the carbon-based thin-film gold nanoparticles with adjustable film thickness prepared in example 18 mainly consist of four elements, i.e., C, O, N, and Au, except for the H element;
6 parts of 1mL of the carbon-based thin-film gold nanoparticles (AuNPs @ CF) prepared in example 18 with a concentration of 0.5mg/mL were added to 6 parts of 1mL of a 10mM TMB solution to obtain 6 parts of a mixed solution, and the pH values of 6 parts of the mixed solution system were adjusted to 5.0, 5.5, 6.0, 6.5, 7.0 and 7.5, respectively; then putting the mixed liquor into an ultrasonic machine for respective ultrasonic treatment for 15 minutes, then respectively filtering the mixed liquor in a water system filter membrane with the diameter of 0.22 mu m, removing unloaded TMB to obtain an AuNPs @ CF-TMB load system, and putting the AuNPs @ CF-TMB load system in 1mM H2O2In solution, the peroxidase-like capacity of CF membranes at different pH was examined, where H2O2Is catalyzed to generate reactive oxygen species that can oxidize colorless TMB to blue OxTMB with increased uv absorption at 650 and 895nm, as shown in fig. 6.
FIG. 6 is a graph of the UV absorption curves for AuNPs @ CF-TMB supported systems at pH 5.0, 5.5, 6.0, 6.5, 7.0, and 7.5;
as can be seen from FIG. 6, the AuNPs @ CF-TMB supported system has better ability to mimic peroxidase with weak acidity.
The AuNPs @ CF-TMB load system is respectively added with hydrogen peroxide at the pH of 5.0, the concentration of the hydrogen peroxide is 0mM, 0.4mM, 0.2mM, 0.8mM, 1.6mM and 3.2mM in sequence, the test is carried out under 980nm laser, and the photoacoustic comparison chart of the AuNPs @ CF-TMB load system with hydrogen peroxide of different concentrations at the pH of 5.0 is shown in figure 7;
FIG. 7 is a photo-acoustic plot of AuNPs @ CF-TMB supported system at different concentrations of hydrogen peroxide at pH 5.0;
the hydrogen peroxide concentration in FIG. 7 was 0mM, 0.4mM, 0.2mM, 0.8mM, 1.6mM and 3.2mM in this order from left to right; AuNPs @ CF-TMB supportUnder weak acid condition to H2O2Have a positive correlation with respect to the catalysis of (a). The weak acid and high hydrogen peroxide concentration are close to the corresponding parameters of the tumor microenvironment, so that the carbon-based nano film regulated load system can be further used for photoacoustic diagnosis of tumors. This example demonstrates the excellent loading capacity of carbon-based thin-film gold nanoparticles and the ability to render the system enzyme-mimetic.
Claims (10)
1. A preparation method of carbon-based thin-film gold nanoparticles with adjustable film thickness is characterized in that the preparation method of the carbon-based thin-film gold nanoparticles with adjustable film thickness is specifically completed according to the following steps:
adding hyaluronic acid into a gold nano solution, and stirring at room temperature to obtain a reaction solution;
secondly, transferring the reaction liquid into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 150-200 ℃, and cooling to room temperature to obtain a reaction product;
III,
Firstly, centrifuging a reaction product, and removing a supernatant to obtain a precipitate; dispersing the precipitated material into distilled water;
and secondly, repeating the third step, and filtering by adopting a 0.22-micron water system microporous filtering membrane to obtain the carbon-based thin film gold nanoparticles with adjustable membrane thickness.
2. The method for preparing carbon-based filmed gold nanoparticles with adjustable membrane thickness according to claim 1, wherein the ratio of the mass of hyaluronic acid to the volume of gold nanoparticle solution in the first step is (10 mg-30 mg):20 mL.
3. The method for preparing carbon-based filmed gold nanoparticles with adjustable membrane thickness according to claim 1, wherein the concentration of the gold nanoparticle solution in the first step is 0.32 mg/mL-0.33 mg/mL; the grain diameter of gold in the gold nanometer solution in the step one is 18.3 nm-21.1 nm.
4. The method for preparing carbon-based filmed gold nanoparticles with adjustable film thickness according to claim 1, wherein the stirring speed in the first step is 1200r/min to 1800r/min, and the stirring time is 0.5h to 1 h.
5. The method for preparing carbon-based thin-film gold nanoparticles with adjustable film thickness according to claim 1, wherein the hydrothermal reaction time in the second step is 2-12 h.
6. The method for preparing carbon-based filmed gold nanoparticles with adjustable membrane thickness according to claim 1, wherein in the second step, the reaction solution is transferred to a hydrothermal reaction kettle, and then hydrothermal reaction is carried out at 160-190 ℃.
7. The method for preparing carbon-based filmed gold nanoparticles with adjustable membrane thickness according to claim 1, wherein in the second step, the reaction solution is transferred to a hydrothermal reaction kettle, and then hydrothermal reaction is carried out at 170-180 ℃.
8. The method for preparing carbon-based filmed gold nanoparticles with adjustable film thickness according to claim 1 or 7, wherein the centrifugation speed in the third step is 7000r/min to 8000r/min, and the centrifugation time is 10min to 20 min; the volume ratio of the mass of the precipitate to the distilled water in the third step (0.40 mg-0.60 mg) is 1 mL.
9. The method for preparing carbon-based filmed gold nanoparticles with adjustable film thickness according to claim 1, wherein the third step is repeated for 3 to 5 times; and step three, the thickness of the carbon-based thin-film gold nanoparticles with adjustable film thickness is 1.39-22.11 nm.
10. Use of a carbon-based filmed gold nanoparticle with adjustable membrane thickness prepared by the preparation method of claim 1, wherein a carbon-based filmed gold nanoparticle with adjustable membrane thickness is used to respond to a tumor microenvironment.
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| CN104162174A (en) * | 2014-07-14 | 2014-11-26 | 东华大学 | Preparation of nano particles with gold coating iron oxide star-shaped core-shell structure, imaging and thermotherapy application thereof |
| CN104368003A (en) * | 2014-11-14 | 2015-02-25 | 郑州大学 | Preparation method and application of hyaluronic acid modified Au-doped titanium dioxide nano-tube |
| CN104548142A (en) * | 2014-12-31 | 2015-04-29 | 东华大学 | Preparation method of hyaluronic acid modified superparamagnetic iron oxide/gold composite nanoprobe |
| CN106044743A (en) * | 2016-06-01 | 2016-10-26 | 郑州轻工业学院 | Preparation method and application of water-soluble carbon quantum dots based on eggshell membranes |
| CN111437388A (en) * | 2019-01-15 | 2020-07-24 | 上海大学 | Gold-silver alloy nano material, preparation method and application thereof |
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