CN114748621A - Crown gold-palladium nano heterogeneous material and preparation method and application thereof - Google Patents
Crown gold-palladium nano heterogeneous material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a coronary gold-palladium nano heterogeneous material and a preparation method and application thereof, belongs to the technical field of photosensitive nano materials, and solves the technical problems that the photodynamic efficiency is low and metastatic cancer cells cannot be completely eliminated when the photothermal/photodynamic synergistic treatment is carried out on cancers. The prepared coronary gold-palladium nano heterogeneous material can effectively improve the photo-thermal and photo-dynamic efficiency of the material, kill in-situ tumor cells, induce the generation of specific cytotoxic T lymphocytes and effectively inhibit the recurrence and metastasis of tumors.
Description
Technical Field
The invention belongs to the technical field of photosensitive nano materials, and particularly relates to a coronary gold-palladium nano heterogeneous material as well as a preparation method and application thereof.
Background
Phototherapy has been widely used in the treatment of malignant tumors, and compared with conventional treatment methods such as surgery, radiotherapy, and chemotherapy, phototherapy has the advantages of non-invasiveness, low toxicity, high targeting property, and low side effects.
Phototherapy, which mainly includes photothermal therapy and photodynamic therapy, is generally used to selectively kill tumor cells under light. PTT typically uses a photothermal agent to generate high temperatures under light to "burn" tumor cells. PDT relies on laser irradiation of a specific wavelength to excite a photosensitizer, which in turn converts the surrounding oxygen molecules into Reactive Oxygen Species (ROS), thereby killing the tumor cells. The combination of photothermal therapy and photodynamic therapy in a diagnostic system may be used to advantage in the treatment of cancer. There are, however, some drawbacks to current nanomaterial phototherapy:
(1) the most common method currently used in phototherapy is to load organic photosensitizers into photothermal materials to achieve PTT/PDT co-therapy, which makes the design cumbersome and not intelligent;
(2) meanwhile, the phototherapy effect of the nano particles with PTT and PDT functions is very low;
(3) and the dead tumor cells can release tumor-associated antigens after phototherapy, and specific Cytotoxic T Lymphocytes (CTL) are induced to generate. CTLs infiltrate into distant tumors, destroying cancer cells. The phototherapy-activated immune cells can secrete a large amount of anti-tumor cytokines, such as interleukin (IL-6), tumor necrosis factor alpha (TNF-alpha), interferon gamma (IFN-gamma), interleukin 12 (IL-12) and the like, and are also involved in killing tumor cells. However, due to insufficient stimulation of the immune system by phototherapy, phototherapy can only eliminate in situ tumors, and cannot completely eliminate metastatic cancer cells.
Inspired by the organism's immune system, nanoparticles with virus-like (spiked particles) can activate and enhance immune responses in vitro and in vivo. The nanopacles exert mechanical stress on the cells, resulting in potassium efflux and inflammasome activation of macrophages and DCs during phagocytosis. The inflammatory corpuscle can regulate the activation of apoptosis protein (caspase-1), further promote the maturation of a cytokine precursor pro-IL-1 beta into IL-1 beta, enhance the cell immune response of antigen specificity and initiate protective immunity aiming at tumor growth. However, this process is rarely reported and finding the best viroid nanomaterials with phototherapeutic properties that can effectively activate the immune system for in situ tumor elimination and effectively inhibit tumor recurrence and metastasis remains a great challenge.
Disclosure of Invention
In order to overcome the defects of the prior art and solve the technical problems that the photodynamic efficiency is low, only in-situ tumors can be eliminated and metastatic cancer cells cannot be completely eliminated when the photothermal/photodynamic synergistic therapy is used for treating cancers, the invention provides a coronary gold-palladium nano heterogeneous material and a preparation method and application thereof.
In order to realize the purpose, the invention is realized according to the following technical scheme:
A crown gold-palladium nano heterogeneous material is characterized in that gold elements exist in the crown gold-palladium nano heterogeneous material in the form of a nano gold rod, palladium elements exist in the form of bulges, the palladium bulges grow on the outer surface of the nano gold rod randomly, and the mass ratio of the gold elements to the palladium elements is 1 (0.1-0.5).
Furthermore, the diameter of the nano gold rod is 10.9nm, the length-diameter ratio is 3.6, and the length of the palladium bump is 11 nm.
Further, the mass ratio of the gold element to the palladium element is 1: 0.3.
A preparation method of a crown gold-palladium nano heterogeneous material comprises the following steps:
s1, adding the cetylpyridinium chloride monohydrate into water, fully stirring and dissolving until the solution is in a transparent state, preparing the cetylpyridinium chloride monohydrate solution with the concentration of 1-100mmol/L, controlling the crown structure of the surface of the gold-palladium nano heterogeneous material, and heating the solution to 65 ℃ for later use;
s2, adding 2mL of sodium tetrachloropalladate solution and 4mL of nano gold rods into the solution heated in the step S1, wherein the concentration of the sodium tetrachloropalladate solution is 10-100mmol/L, and controlling NaPdCl4Adjusting the plasma resonance absorption peak of the mixed solution to be close to 800 nanometers, wherein the light absorption value of the nano gold rod is 1, the diameter is 10.9nm, and the length-diameter ratio is 3.6;
S3, adding a fresh ascorbic acid solution with the concentration of 100mmol/L into the mixed solution prepared in the step S2, rapidly stirring for 2 minutes, and then keeping the mixture standing for 2 hours at a constant temperature of 65 ℃;
s4, centrifuging the mixed solution obtained in the step S3 to obtain nano particles, and then washing the nano material for at least 3 times by water to obtain the coronary gold-palladium nano heterostructure material.
Further, in the step S2, the gold nanorods are prepared by a method of seed-mediated growth, including the steps of:
s2-1, preparing gold element seed solution:
adding 0.25mL of 10mmol/L tetrachloroauric acid into 5mL of 200mmol/L hexadecyl trimethyl ammonium bromide solution to prepare a seed solution for the next step;
s2-2, preparing growth solution
Weighing 3.08g of hexadecyl trimethyl ammonium chloride and 0.77g of sodium oleate, adding into 250mL of water, and heating to dissolve until the solution is transparent;
keeping the heating temperature of the mixed solution in the step I, adding 6mL of silver nitrate with the concentration of 4mmol/L and 250mL of tetrachloroauric acid with the concentration of 5mmol/L, and stirring for 150 minutes at 30 ℃ until the solution is colorless and transparent;
③ adding 2mL of hydrochloric acid solution with the concentration of 37wt% into the colorless transparent solution prepared in the step (II), and stirring for 15 minutes;
Fourthly, firstly, adding 0.6mL of 10mmol/L sodium borohydride solution into the seed solution prepared in the step S2-1 under the condition of vigorous stirring, and aging the obtained brown yellow solution for 30 minutes at the temperature of 30 ℃; meanwhile, 0.62mL of ascorbic acid solution with the concentration of 64mmol/L is added into the solution prepared in the step (c), and the mixture is stirred vigorously for 30 seconds; finally, quickly injecting 0.4-0.6 mL of aged seed solution into the mixed solution;
fifthly, stirring the solution prepared in the step IV for 1 minute, standing overnight at the temperature of 30 ℃ to grow the nano-gold rod.
Further, in the fourth step, the length-diameter ratio of the Au nanorods is adjusted by adjusting the content of the seed solution.
Further, in the step S4, the centrifugation rotation speed is 7000rpm, and the centrifugation time is 10 minutes.
The invention also provides an application of the coronary gold-palladium nano heterogeneous material prepared by the method, and the coronary gold-palladium nano heterogeneous material is used in a medicament for killing in-situ tumor cells and inhibiting tumor recurrence and metastasis under the near infrared light excitation condition.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a method for simply, efficiently and conveniently synthesizing a crown gold-palladium nano heterogeneous material. The synthesized gold-palladium crown nano heterogeneous material has strong near infrared light absorption capacity, and can effectively promote the separation of electrons and holes under the irradiation of near infrared light, thereby effectively improving the photo-thermal and photodynamic efficiency of the material and effectively killing in-situ tumor cells. The burr property of the coronary gold-palladium nano heterojunction and a large amount of tumor-related antigens generated after phototherapy can promote the maturation and activation of dendritic cells, further induce the generation of specific cytotoxic T lymphocytes and effectively inhibit the recurrence and metastasis of tumors.
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The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a transmission electron microscope photograph of a crown gold-palladium nano heterogeneous material;
FIG. 2 is a diagram of an absorption spectrum of the gold-palladium nano heterogeneous material, which is sequentially formed by ultraviolet light, visible light and near infrared light from left to right;
FIG. 3 is a photo-thermal temperature rise curve of the gold-palladium nano heterogeneous material under 808nm near infrared light irradiation;
FIG. 4 is a graph of the active oxygen free radicals (i.e. the photodynamic performance) generated by the crown gold-palladium nano heterogeneous material under the irradiation of near infrared light at 808 nm;
FIG. 5 is a flow data diagram of dendritic cell maturation and activation promoted by the burr nature of the coronary gold-palladium nano heterogeneous material, and the expression of co-stimulatory molecules (CD 80, CD 86) is a mark of DC maturation;
fig. 6 is a flow chart of a large number of tumor associated antigens generated by the coronary gold-palladium nano heterogeneous material after phototherapy to promote maturation and activation of dendritic cells;
FIG. 7 is a biosafety test chart of the coronary gold-palladium nano heterogeneous material;
FIG. 8 is a test chart of the killing ability of the coronary gold-palladium nano heterogeneous material to tumor cells;
fig. 9 is a transmission electron microscope photograph of the gold-palladium nano heterogeneous material prepared in example 2.
FIG. 10 is a TEM image of the coronal Au-Pd nanolithography material prepared in example 3.
Detailed Description
The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention. Unless otherwise specified, the examples follow conventional experimental conditions. In addition, it will be apparent to those skilled in the art that various modifications or improvements may be made in the material composition and the amount of the components in the embodiments without departing from the spirit and scope of the invention as defined in the appended claims.
Example 1
The invention provides a coronary gold-palladium nano heterogeneous material which has the capacity of photo-thermal and photodynamic cooperative therapy to kill in-situ tumors, induces specific cytotoxic T lymphocytes to generate by utilizing the burr property of the material and a large amount of tumor-related antigens generated after phototherapy, and effectively inhibits the recurrence and metastasis of the tumors. Wherein the diameter of the nano gold rod is 10.9nm, the length-diameter ratio is 3.6, the length of the palladium bulge is 11nm,
a preparation method of a crown gold-palladium nano heterogeneous material comprises the following steps:
s1, adding the cetylpyridinium chloride monohydrate into water, fully stirring and dissolving until the solution is transparent, preparing the cetylpyridinium chloride monohydrate solution with the concentration of 1mmol/L, and heating the solution to 65 ℃ for later use;
S2, adding 2mL of sodium tetrachloropalladate solution and 4mL of nano gold rods into the solution heated in the step S1, wherein the concentration of the sodium tetrachloropalladate solution is 50mmol/L, the light absorption value of the nano gold rods is 1, the diameter is 10.9nm, and the length-diameter ratio is 3.6;
the method is characterized in that the gold nanorod is prepared by a seed-mediated growth method and comprises the following steps:
s2-1, preparing gold element seed solution:
adding 0.25mL of 10mmol/L tetrachloroauric acid into 5mL of 200mmol/L hexadecyl trimethyl ammonium bromide solution to prepare a seed solution for later use;
s2-2, preparing growth solution
Weighing 3.08g of hexadecyltrimethylammonium chloride and 0.77g of sodium oleate, adding the hexadecyltrimethylammonium chloride and the 0.77g of sodium oleate into 250mL of water, and heating to dissolve until the solution is transparent;
keeping the heating temperature of the mixed solution in the step I, adding 6mL of silver nitrate with the concentration of 4mmol/L and 250mL of tetrachloroauric acid with the concentration of 5mmol/L, and stirring for 150 minutes at 30 ℃ until the solution is colorless and transparent;
thirdly, adding 2mL of hydrochloric acid solution with the concentration of 37wt% into the colorless transparent solution prepared in the second step, and stirring for 15 minutes;
fourthly, firstly, adding 0.6mL of 10mmol/L sodium borohydride solution into the seed solution prepared in the step S2-1 under vigorous stirring, and aging the obtained brown yellow solution for 30 minutes at 30 ℃; meanwhile, 0.62mL of ascorbic acid solution with the concentration of 64mmol/L is added into the solution prepared in the step (c), and the mixture is stirred vigorously for 30 seconds; finally, 0.4mL of aged seed solution is quickly injected into the mixed solution, and the length-diameter ratio of the Au nanorod is adjusted by adjusting the content of the seed solution;
Fifthly, stirring the solution prepared in the step IV for 1 minute, standing overnight at the temperature of 30 ℃ to grow the nano-gold rod.
S3, adding a fresh ascorbic acid solution with the concentration of 100mmol/L into the mixed solution prepared in the step S2, quickly stirring for 2 minutes, and then keeping the mixed solution at the constant temperature of 65 ℃ for standing for 2 hours;
s4, centrifuging the mixed solution prepared in the step S3 to obtain nano particles, wherein the centrifugal speed is 7000rpm, and the centrifugal time is 10 minutes; and then the nano material is washed for at least 3 times by water to prepare the coronary gold-palladium nano heterostructure material.
In the coronary gold-palladium nano heterostructure material prepared in the embodiment 1, the mass ratio of the gold element to the palladium element is 1:0.3, and the length of the palladium bump is 11 nm.
Performance test experiment of the coronal gold-palladium nano heterogeneous material prepared in this example 1:
the photo-thermal capability test of the coronary gold-palladium nano heterogeneous material comprises the following steps:
1) 1 mL of coronary gold-palladium nano heterogeneous material (100 mu g mL) is taken-1) Fixing in a quartz cuvette;
2) using 808 nm laser at 0.75W cm-2Irradiating the solution for 10 minutes at the power of (1);
3) in the irradiation process, recording a temperature value once every 30 seconds for drawing a photothermal curve;
secondly, testing the photodynamic performance of the crown gold-palladium nano heterogeneous material:
1) Mixing 20. mu.L of the coronary gold palladium nano heterojunction material (100. mu.g/mL) with 80. mu.L of 2 ', 7' -dichlorofluorescein diacetate (DCFH-DA, 29. mu.M);
2) using 808 nm laser at 0.75W cm-2Irradiating the solution for 10 minutes;
3) after 24 hours of co-incubation, collecting the fluorescence emission spectrum of DCF within 500-600nm at the excitation wavelength of 490 nm;
thirdly, in-vitro immunostimulation of dendritic cells by the coronary gold-palladium nano heterojunction material:
1) dendritic cells were isolated from bone marrow of BALB/c mice of about 8 weeks of age and cultured in RPMI-1640 medium containing 10% fetal bovine serum, penicillin (100. mu.g/mL), streptomycin (100. mu.g/mL), GM-CSF (10 ng/mL), and IL-4 (10 ng/mL);
2) culturing the dendritic cells at 1.6 × 105Cell density per well seeded in 6-well plates at 37 ℃ and 5% CO2Growing overnight under the atmosphere;
3) remove the upper layer of the medium and add 100. mu.g mL-1Incubating the coronary gold-palladium nano heterojunction materials for 24 hours;
4) gently washing the cells three times with PBS, staining the DCs with antibodies labeled with CD80 and CD86, and detecting the maturation degree of the DCs by a flow cytometer;
fourthly, in vitro immunostimulation of the phototherapy on dendritic cells:
1) Inoculating dendritic cells of bone marrow sources separated from BALB/c mice into a Transwell lower cavity, and inoculating a coronary gold-palladium nano heterojunction material and 4T1 cells into an upper cavity after co-incubation;
2) using 808nm laser at 0.75W cm-2Is irradiated for 10 minutes;
3) after the co-culture for 6 hours, gently washing the cells with PBS three times, staining the DC with antibodies marked by CD80 and CD86, and detecting the maturity of the DC by a flow cytometer;
and fifthly, testing the biocompatibility of the coronary gold-palladium nano heterogeneous material:
1) mouse breast cancer cell 4T1 cells at 1X 104Cell density per well seeded in 96-well plates at 37oC and 5% CO2Growing overnight under the atmosphere;
2) the upper medium was removed and 100. mu.L of fresh medium containing 6.25, 12.5, 25, 50 and 100. mu.g mL of medium was added-1 Incubating the gold-palladium nano heterojunction materials for 24 hours;
3) add 20. mu.L of 5 mg mL to each well-1The MTT solution of (5), incubated for 3.5 hours;
4) the cell culture medium was removed and 150 μ L DMSO was added to each well. Then after shaking the plate for 10 minutes, the absorbance at 490 nm was measured to calculate the cell activity;
sixthly, a killing experiment of the coronary gold-palladium nano heterogeneous material on tumor cells under 808nm laser irradiation:
1) Mouse breast cancer cell 4T1 cells at 1X 104Cell density per well seeded in 96-well plates at 37oC and 5% CO2Growing overnight under the atmosphere;
2) the upper medium was removed and 100. mu.L of fresh medium containing 6.25, 12.5, 25, 50 and 100. mu.g mL of medium was added-1 Incubating the gold-palladium nano heterojunction materials for 6 hours;
3) after incubation for 6 hours, the cells were incubated with a 808nm laser (0.75W cm)-2) Cells were irradiated for 10 minutes and incubated for an additional 18 hours;
4) add 20. mu.L of 5 mg mL to each well-1The MTT solution of (5), incubated for 3.5 hours;
5) the cell culture medium was removed and 150 μ L DMSO was added to each well. Then, after shaking the plate for 10 minutes, absorbance at 490 nm was measured to calculate cell activity.
FIG. 1 is a TEM photograph of the crown-shaped Au-Pd nano-heterogeneous material prepared in example 1, and it can be seen from FIG. 1 that the diameter of the Au nano-rod is 10.9nm, the length-diameter ratio is 3.6, and the length of the Pd bump is 11 nm. The surface successfully synthesizes the crown gold-palladium nano heterogeneous material with uniform size.
FIG. 2 is an absorption spectrum of the crown Au-Pd nano-heterogeneous material prepared in example 1, and it can be seen from FIG. 1 that the absorption peak of the crown Au-Pd nano-heterogeneous material is located near 808 nm.
FIG. 3 is a photo-thermal temperature rise graph of the crown gold-palladium nano heterogeneous material prepared in example 1 under 808nm near-infrared light irradiation. As can be seen from figure 3, under the laser irradiation of 808nm, the temperature is stably increased, which shows that the crown gold-palladium nano heterogeneous material has good photo-thermal conversion performance.
FIG. 4 is a graph showing the generation of active oxygen radicals under 808nm near infrared light irradiation of the gold-palladium nano heterogeneous material prepared in example 1. As can be seen from figure 4, the crown gold-palladium nano heterogeneous material can cause remarkable increase of fluorescence intensity under the near infrared light irradiation of 808nm, which shows that active oxygen free radicals are generated efficiently, and the excellent photodynamic performance is shown.
Fig. 5 is a flow chart of the flow data of the dendritic cells maturation and activation promoted by the burr nature of the coronary gold-palladium nano heterogeneous material prepared in example 1, and the expression of costimulatory molecules (CD 80, CD 86) is a sign of DC maturation. The results show that the coronary gold-palladium nano heterogeneous material can induce dendritic cells to mature per se, which means that the coronary gold-palladium nano heterogeneous material has the potential to induce immune response.
Fig. 6 is a schematic diagram (fig. 6A) and a flow data chart (fig. 6B) of the massive tumor-associated antigens generated by the coronary gold-palladium nano heterogeneous material prepared in example 1 after phototherapy to promote the maturation and activation of dendritic cells. The results demonstrate that 4T1 cell debris can significantly increase dendritic cell maturation after phototherapy.
Fig. 7 is a biosafety test chart of the coronary gold-palladium nano heterogeneous material prepared in example 1. The results show that after the coronary gold-palladium nano heterogeneous material is incubated for 24 hours by 4T1 cells, the cell survival rate is over 80 percent, the surface has good biocompatibility, and the coronary gold-palladium nano heterogeneous material can be used for cell and in vivo experiments.
Fig. 8 is a test chart of the ability of the coronary gold-palladium nano heterogeneous material prepared in example 1 to kill tumor cells under near infrared light excitation. The MTT result shows that the coronary gold-palladium nano heterogeneous material presents the tumor cell killing capability of concentration dependence under the near infrared light excitation, which indicates that the coronary gold-palladium nano heterogeneous material prepared by the method can be used for killing the tumor cells under the near infrared light excitation condition.
Example 2
A preparation method of a crown gold-palladium nano heterogeneous material comprises the following steps:
s1, adding the cetylpyridinium chloride monohydrate into water, fully stirring and dissolving until the solution is transparent, preparing the cetylpyridinium chloride monohydrate solution with the concentration of 1mmol/L, and heating the solution to 65 ℃ for later use;
s2, adding 2mL of sodium tetrachloropalladate solution and 4mL of nano gold rods into the solution heated in the step S1, wherein the concentration of the sodium tetrachloropalladate solution is 10mmol/L, the light absorption value of the nano gold rods is 1, the diameter is 10.9nm, and the length-diameter ratio is 3.6;
The method is characterized in that the gold nanorod is prepared by a seed-mediated growth method and comprises the following steps:
s2-1, preparing gold element seed solution:
adding 0.25mL of 10mmol/L tetrachloroauric acid into 5mL of 200mmol/L hexadecyl trimethyl ammonium bromide solution to prepare a seed solution for the next step;
s2-2, preparing growth solution
Weighing 3.08g of hexadecyl trimethyl ammonium chloride and 0.77g of sodium oleate, adding into 250mL of water, and heating to dissolve until the solution is transparent;
keeping the heating temperature of the mixed solution in the step I, adding 6mL of silver nitrate with the concentration of 4mmol/L and 250mL of tetrachloroauric acid with the concentration of 5mmol/L, and stirring for 150 minutes at 30 ℃ until the solution is colorless and transparent;
③ adding 2mL of hydrochloric acid solution with the concentration of 37wt% into the colorless transparent solution prepared in the step (II), and stirring for 15 minutes;
fourthly, firstly, adding 0.6mL of 10mmol/L sodium borohydride solution into the seed solution prepared in the step S2-1 under vigorous stirring, and aging the obtained brown yellow solution for 30 minutes at 30 ℃; meanwhile, 0.62mL of ascorbic acid solution with the concentration of 64mmol/L is added into the solution prepared in the third step, and the mixture is stirred vigorously for 30 seconds; finally, 0.4mL of aged seed solution is quickly injected into the mixed solution, and the length-diameter ratio of the Au nanorod is adjusted by adjusting the content of the seed solution;
Fifthly, stirring the solution prepared in the step IV for 1 minute, standing overnight at the temperature of 30 ℃ to grow the nano-gold rod.
S3, adding a fresh ascorbic acid solution with the concentration of 100mmol/L into the mixed solution prepared in the step S2, rapidly stirring for 2 minutes, and then keeping the mixture standing for 2 hours at a constant temperature of 65 ℃;
s4, centrifuging the mixed solution prepared in the step S3 to obtain nano particles, wherein the centrifugal speed is 7000rpm, and the centrifugal time is 10 minutes; and then the nano material is washed for at least 3 times by water to prepare the coronary gold-palladium nano heterostructure material.
A crown gold-palladium nano heterogeneous material, in this example 2, the mass ratio of gold element to palladium element is 1: 0.1.
In the material of the crown gold-palladium nano heterostructure prepared in the embodiment 2, the mass ratio of the gold element to the palladium element is 1:0.1, and the length of the palladium bump is 5 nm.
Fig. 9 is a transmission electron microscope photograph of the coronally formed gold-palladium nano heterogeneous material prepared in example 2, and it is observed that the coronally formed gold-palladium nano heterogeneous material is successfully prepared and has a uniform structure.
The gold-palladium nano heterogeneous material prepared in this embodiment 2 has the photo-thermal, photodynamic and dendritic cell maturation stimulating capabilities prepared in embodiment 1, and can also effectively kill tumor cells.
Example 3
A preparation method of a crown gold-palladium nano heterogeneous material comprises the following steps:
s1, adding the cetylpyridinium chloride monohydrate into water, fully stirring and dissolving until the solution is transparent, preparing the cetylpyridinium chloride monohydrate solution with the concentration of 1mmol/L, and heating the solution to 65 ℃ for later use;
s2, adding 2mL of sodium tetrachloropalladate solution and 4mL of nano gold rods into the solution heated in the step S1, wherein the concentration of the sodium tetrachloropalladate solution is 100mmol/L, the light absorption value of the nano gold rods is 1, the diameter is 10.9nm, and the length-diameter ratio is 3.6;
the method is characterized in that the gold nanorod is prepared by a seed-mediated growth method and comprises the following steps:
s2-1, preparing gold element seed solution:
adding 0.25mL of 10mmol/L tetrachloroauric acid into 5mL of 200mmol/L hexadecyl trimethyl ammonium bromide solution to prepare a seed solution for later use;
s2-2, preparing growth solution
Weighing 3.08g of hexadecyltrimethylammonium chloride and 0.77g of sodium oleate, adding the hexadecyltrimethylammonium chloride and the 0.77g of sodium oleate into 250mL of water, and heating to dissolve until the solution is transparent;
keeping the heating temperature of the mixed solution in the step I, adding 6mL of silver nitrate with the concentration of 4mmol/L and 250mL of tetrachloroauric acid with the concentration of 5mmol/L, and stirring for 150 minutes at the temperature of 30 ℃ until the solution is colorless and transparent;
Thirdly, adding 2mL of hydrochloric acid solution with the concentration of 37wt% into the colorless transparent solution prepared in the second step, and stirring for 15 minutes;
fourthly, firstly, adding 0.6mL of 10mmol/L sodium borohydride solution into the seed solution prepared in the step S2-1 under the condition of vigorous stirring, and aging the obtained brown yellow solution for 30 minutes at the temperature of 30 ℃; meanwhile, 0.62mL of ascorbic acid solution with the concentration of 64mmol/L is added into the solution prepared in the step (c), and the mixture is stirred vigorously for 30 seconds; finally, 0.4mL of aged seed solution is quickly injected into the mixed solution, and the length-diameter ratio of the Au nanorod is adjusted by adjusting the content of the seed solution;
fifthly, stirring the solution prepared in the step IV for 1 minute, standing overnight at the temperature of 30 ℃ to grow, and preparing the nano gold rod.
S3, adding a fresh ascorbic acid solution with the concentration of 100mmol/L into the mixed solution prepared in the step S2, quickly stirring for 2 minutes, and then keeping the mixed solution at the constant temperature of 65 ℃ for standing for 2 hours;
s4, centrifuging the mixed solution prepared in the step S3 to obtain nano particles, wherein the centrifugal speed is 7000rpm, and the centrifugal time is 10 minutes; and then the nano material is washed for at least 3 times by water to prepare the coronary gold-palladium nano heterostructure material.
A crown gold-palladium nano heterogeneous material, in this example 3, the mass ratio of gold element to palladium element is 1: 0.5.
In the coronal au-pd nano heterostructure material prepared in this example 3, the mass ratio of au element to pd element was 1: 0.5, and the length of the pd bump was 13 nm.
Fig. 10 is a transmission electron microscope photograph of the coronally formed gold-palladium nano heterogeneous material prepared in example 3, and it is observed that the coronally formed gold-palladium nano heterogeneous material is successfully prepared and has a uniform structure.
The coronary gold-palladium nano heterogeneous material prepared in the embodiment has photo-thermal and photodynamic capacity and capability of stimulating dendritic cells to mature, and can also effectively kill tumor cells.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (8)
1. A crown gold-palladium nano heterogeneous material is characterized in that: the gold element in the crown gold-palladium nano heterogeneous material exists in a nano gold rod, the palladium element exists in a bulge, the palladium bulge grows on the outer surface of the nano gold rod randomly, and the mass ratio of the gold element to the palladium element is 1 (0.1-0.5).
2. The crown gold-palladium nano heterogeneous material as claimed in claim 1, wherein: the diameter of the nano gold rod is 10.9nm, the length-diameter ratio is 3.6, and the length of the palladium bulge is 11 nm.
3. The crown gold-palladium nano heterogeneous material as claimed in claim 1, wherein: the mass ratio of the gold element to the palladium element is 1: 0.3.
4. A method for preparing the crown gold-palladium nano heterogeneous material as claimed in claim 1, which is characterized by comprising the following steps:
s1, adding the cetylpyridinium chloride monohydrate into water, fully stirring and dissolving until the solution is in a transparent state, preparing the cetylpyridinium chloride monohydrate solution with the concentration of 1-100mmol/L, and heating the solution to 65 ℃ for later use;
s2, adding 2mL of sodium tetrachloropalladate solution and 4mL of nano gold rod into the solution heated in the step S1, wherein the concentration of the sodium tetrachloropalladate solution is 10-100mmol/L, the light absorption value of the nano gold rod is 1, the diameter is 10.9nm, and the length-diameter ratio is 3.6;
s3, adding a fresh ascorbic acid solution with the concentration of 100mmol/L into the mixed solution prepared in the step S2, quickly stirring for 2 minutes, and then keeping the mixed solution at the constant temperature of 65 ℃ for standing for 2 hours;
s4, centrifuging the mixed solution obtained in the step S3 to obtain nano particles, and then washing the nano material for at least 3 times by water to obtain the coronary gold-palladium nano heterostructure material.
5. The method for preparing a crown gold-palladium nano heterogeneous material according to claim 4, wherein the method comprises the following steps:
in step S2, the gold nanorods are prepared by a method of seed-mediated growth, including the steps of:
s2-1, preparing gold element seed solution:
adding 0.25mL of 10mmol/L tetrachloroauric acid into 5mL of 200mmol/L hexadecyl trimethyl ammonium bromide solution to prepare a seed solution for later use;
s2-2, preparing growth solution
Weighing 3.08g of hexadecyl trimethyl ammonium chloride and 0.77g of sodium oleate, adding into 250mL of water, and heating to dissolve until the solution is transparent;
keeping the heating temperature of the mixed solution in the step I, adding 6mL of silver nitrate with the concentration of 4mmol/L and 250mL of tetrachloroauric acid with the concentration of 5mmol/L, and stirring for 150 minutes at 30 ℃ until the solution is colorless and transparent;
③ adding 2mL of hydrochloric acid solution with the concentration of 37wt% into the colorless transparent solution prepared in the step (II), and stirring for 15 minutes;
fourthly, firstly, adding 0.6mL of 10mmol/L sodium borohydride solution into the seed solution prepared in the step S2-1 under vigorous stirring, and aging the obtained brown yellow solution for 30 minutes at 30 ℃; meanwhile, 0.62mL of ascorbic acid solution with the concentration of 64mmol/L is added into the solution prepared in the third step, and the mixture is stirred vigorously for 30 seconds; finally, quickly injecting 0.4-0.6 mL of aged seed solution into the mixed solution;
Fifthly, stirring the solution prepared in the step IV for 1 minute, standing overnight at the temperature of 30 ℃ to grow the nano-gold rod.
6. The method for preparing a crown gold-palladium nano heterogeneous material according to claim 5, wherein the method comprises the following steps: in the step IV, the length-diameter ratio of the nano gold rod is adjusted by adjusting the content of the seed solution.
7. The method for preparing a crown gold-palladium nano heterogeneous material according to claim 6, wherein the method comprises the following steps: in step S4, the centrifugation speed was 7000rpm and the centrifugation time was 10 minutes.
8. The use of the crown gold-palladium nano heterogeneous material as claimed in claim 1, wherein: the gold-palladium nano heterogeneous material is used for killing in-situ tumor cells and inhibiting tumor recurrence and metastasis under the near infrared light excitation condition.
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