CN114748621B - 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 provides a coronary gold-palladium nano heterogeneous material and a preparation method and application thereof, which belong to the technical field of photosensitive nano materials and solve the technical problems that the photodynamic efficiency is low and metastatic cancer cells cannot be completely cleared when the photothermal/photodynamic is used for cooperatively treating cancers. The prepared coronary gold-palladium nano heterogeneous material can effectively improve the photo-thermal and photodynamic efficiency of the material, kill in-situ tumor cells, induce specific cytotoxic T lymphocyte generation 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 crown gold-palladium nano heterogeneous material and a preparation method and application thereof.
Background
Phototherapy has been widely used for the treatment of malignant tumors, and has the advantages of non-invasiveness, low toxicity, high targeting, small side effects and the like compared with conventional treatment means such as surgery, radiotherapy, chemotherapy and the like.
Phototherapy, mainly comprising photothermal therapy and photodynamic therapy, usually uses phototherapeutic agents to selectively kill tumor cells under light. PTT generally uses photothermal agents to generate high temperatures under light to "burn" tumor cells. PDT relies on laser irradiation at a specific wavelength to excite the photosensitizer, which in turn converts surrounding oxygen molecules into Reactive Oxygen Species (ROS), thereby killing tumor cells. The combination of photothermal therapy and photodynamic therapy with the synergistic effect of the two can be well used for treating cancer in a diagnostic system. However, nanomaterial phototherapy has some disadvantages:
(1) The most commonly used method in phototherapy at present is to load organic photosensitizer into a photo-thermal material to realize PTT/PDT cooperative therapy, thus making the design complicated and not intelligent;
(2) The phototherapy effect of the nano-particles with PTT and PDT functions is very low;
(3) Tumor cells that die after phototherapy can release tumor-associated antigens, inducing the production of specific Cytotoxic T Lymphocytes (CTLs). CTL 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 also participate in killing tumor cells. However, because phototherapy has insufficient stimulation to the immune system, current phototherapy can only eliminate in-situ tumors and cannot completely eliminate metastatic cancer cells.
Nanoparticles with viroids (spike particles) can activate and enhance immune responses in vitro and in vivo, inspired by the immune system of the organism. The nanonails exert mechanical stress on the cells, resulting in potassium efflux and inflammatory body activation of macrophages and DCs during phagocytosis. The inflammatory minibody is capable of modulating activation of the apoptosis protein (caspase-1), thereby promoting maturation of the cytokine precursor pro-IL-1β to IL-1β, enhancing antigen-specific cellular immune responses, and eliciting protective immunity against tumor growth. However, this process has rarely been reported, and finding optimal viral nanomaterials that have phototherapy properties and that can effectively activate the immune system for in situ tumor elimination and effectively inhibit tumor recurrence and metastasis remains a significant challenge.
Disclosure of Invention
In order to overcome the defects of the prior art, solve the technical problems that the photodynamic efficiency is low and only in-situ tumors can be eliminated and metastatic cancer cells can not be completely eliminated when the photothermal/photodynamic synergistic treatment 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 achieve the above object, the present invention is realized according to the following technical scheme:
a coronary gold-palladium nano heterogeneous material, wherein the existence form of gold element in the coronary gold-palladium nano heterogeneous material is a nano gold rod, the existence form of palladium element is a bulge, the palladium bulge grows on the outer surface of the nano gold rod irregularly, and the mass ratio of the gold element to the palladium element is 1 (0.1-0.5).
Further, 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 11nm.
Further, the mass ratio of the gold element to the palladium element is 1:0.3.
The preparation method of the coronary gold-palladium nano heterogeneous material comprises the following steps:
s1, adding cetyl pyridine chloride monohydrate into water, fully stirring and dissolving until the solution is in a transparent state, preparing cetyl pyridine chloride monohydrate solution with the concentration of 1-100mmol/L, controlling the crown structure of the surface of a gold-palladium nano heterogeneous material, and then heating the solution to 65 ℃ for later use;
s2, heating the solution in the step S1Adding 2mL of sodium tetrachloropalladate solution and 4mL of nano gold rod, wherein the concentration of the sodium tetrachloropalladate solution is 10-100mmol/L, and controlling NaPdCl 4 The plasma resonance absorption peak of the mixed solution is regulated to be close to 800 nanometers, the absorption value of the nano gold rod is 1, the diameter is 10.9nm, and the length-diameter ratio is 3.6;
s3, adding 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 constant temperature of 65 ℃ for standing for 2 hours;
and S4, centrifuging the mixed solution prepared in the step S3 to obtain nano particles, and then washing the nano material with water for at least 3 times to obtain the crown gold-palladium nano heterostructure material.
Further, in the step S2, the nano gold rod is prepared by a seed-mediated growth method, and the method comprises the following steps:
s2-1, preparing a gold element seed solution:
adding 0.25mL of tetrachloroauric acid with the concentration of 10mmol/L into 5mL of cetyltrimethylammonium bromide solution with the concentration of 200mmol/L to prepare seed solution for later use;
s2-2, preparation of growth solution
(1) 3.08g of cetyltrimethylammonium chloride and 0.77g of sodium oleate are weighed and added into 250mL of water, and heated and dissolved until the solution is transparent;
(2) maintaining the heating temperature of the mixed solution in the step (1), adding 6mL of silver nitrate with the concentration of 4mmol/L and 250mL of tetrachloroauric acid with the concentration of 5mmol/L into the mixed solution, and stirring the mixed solution at the temperature of 30 ℃ for 150 minutes until the solution is colorless and transparent;
(3) adding 2mL of 37wt% hydrochloric acid solution into the colorless transparent solution prepared in the step (2), and stirring for 15 minutes;
(4) firstly, adding 0.6mL of sodium borohydride solution with the concentration of 10mmol/L into the seed solution prepared in the step S2-1 under intense stirring, and aging the obtained brown yellow solution at 30 ℃ for 30 minutes; meanwhile, adding 0.62mL of ascorbic acid solution with the concentration of 64mmol/L into the solution prepared in the step (3), and vigorously stirring for 30 seconds; finally, 0.4-0.6 mL of the aged seed solution is quickly injected into the mixed solution;
(5) stirring the solution prepared in the step (4) for 1 minute, and standing at 30 ℃ for overnight growth to prepare the nano gold rod.
Further, in the step (4), the length-diameter ratio of the Au nanorods is adjusted by adjusting the added content of the seed solution.
Further, in the step S4, the centrifugal speed was 7000rpm and the centrifugal time was 10 minutes.
The invention also provides 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 simple, efficient and convenient method for synthesizing a crown gold-palladium nano heterogeneous material. The synthesized crown gold-palladium nano heterogeneous material has strong near infrared light absorption capability, and can effectively promote the separation of electrons and holes under the irradiation of near infrared light, so that the photo-thermal and photodynamic efficiency of the material is effectively improved, and in-situ tumor cells can be effectively killed. The burr property of the crown 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.
Drawings
The invention is described in further detail below with reference to the drawings and the detailed description.
FIG. 1 is a transmission electron micrograph of a gold-palladium coronal nanoscopic heterogeneous material;
FIG. 2 is an absorption spectrum diagram of a crown gold-palladium nano heterogeneous material, wherein ultraviolet light, visible light and near infrared light are sequentially arranged from left to right in the diagram;
FIG. 3 is a photo-thermal heating graph of a crown gold-palladium nano-heterogeneous material under 808nm near infrared light irradiation;
FIG. 4 is a graph of the generation of reactive oxygen species (i.e., photodynamic properties) of a gold-palladium crown nanomaterial under near infrared light illumination at 808 nm;
FIG. 5 is a flow chart of data of the nature of burrs carried by the gold-palladium coronal nanomaterial itself to promote maturation and activation of dendritic cells, the expression of costimulatory molecules (CD 80, CD 86) being a marker of DC maturation;
FIG. 6 is a flow chart of data for the maturation and activation of dendritic cells promoted by a number of tumor-associated antigens produced by a gold-palladium coronal nanomaterial following phototherapy;
FIG. 7 is a graph of biosafety testing of a coronal gold-palladium nano-heterogeneous material;
FIG. 8 is a graph showing the killing ability of a gold-palladium coronal nano-heterogeneous material to tumor cells;
fig. 9 is a transmission electron micrograph of the crown gold-palladium nano heterogeneous material prepared in example 2.
Fig. 10 is a transmission electron micrograph of the crown gold-palladium nano heterogeneous material prepared in example 3.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention. Unless otherwise indicated, the examples were all under conventional experimental conditions. In addition, various modifications or improvements in the materials ingredients and amounts used in these embodiments will be apparent to those skilled in the art without departing from the spirit and scope of the invention, and are intended to be within the scope of the invention as claimed.
Example 1
The invention provides a coronary gold-palladium nano heterogeneous material which has the capability of photo-thermal and photodynamic synergistic treatment to kill in-situ tumors, and utilizes the burr property of the material and the generation of a large number of tumor-related antigens induced by phototherapy to generate specific cytotoxic T lymphocytes so as to effectively inhibit 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 bump is 11nm,
the preparation method of the coronary gold-palladium nano heterogeneous material comprises the following steps:
s1, adding cetyl pyridine chloride monohydrate into water, fully stirring and dissolving until the solution is in a transparent state, preparing cetyl pyridine chloride monohydrate solution with the concentration of 1mmol/L, and then 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 50mmol/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;
the nano gold rod is prepared by a seed-mediated growth method, and comprises the following steps:
s2-1, preparing a gold element seed solution:
adding 0.25mL of tetrachloroauric acid with the concentration of 10mmol/L into 5mL of cetyltrimethylammonium bromide solution with the concentration of 200mmol/L to prepare seed solution for later use;
s2-2, preparation of growth solution
(1) 3.08g of cetyltrimethylammonium chloride and 0.77g of sodium oleate are weighed and added into 250mL of water, and heated and dissolved until the solution is transparent;
(2) maintaining the heating temperature of the mixed solution in the step (1), adding 6mL of silver nitrate with the concentration of 4mmol/L and 250mL of tetrachloroauric acid with the concentration of 5mmol/L into the mixed solution, and stirring the mixed solution at the temperature of 30 ℃ for 150 minutes until the solution is colorless and transparent;
(3) adding 2mL of 37wt% hydrochloric acid solution into the colorless transparent solution prepared in the step (2), and stirring for 15 minutes;
(4) firstly, adding 0.6mL of sodium borohydride solution with the concentration of 10mmol/L into the seed solution prepared in the step S2-1 under intense stirring, and aging the obtained brown yellow solution at 30 ℃ for 30 minutes; meanwhile, adding 0.62mL of ascorbic acid solution with the concentration of 64mmol/L into the solution prepared in the step (3), and vigorously stirring for 30 seconds; finally, 0.4mL of the aged seed solution is quickly injected into the mixed solution, and the length-diameter ratio of the Au nano-rod is adjusted by adjusting the added content of the seed solution;
(5) stirring the solution prepared in the step (4) for 1 minute, and standing at 30 ℃ for overnight growth to prepare the nano gold rod.
S3, adding 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 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 with water for at least 3 times to prepare the crown-shaped gold-palladium nano heterostructure material.
In the crown gold-palladium nano heterostructure material prepared in the embodiment 1, the mass ratio of gold element to palladium element is 1:0.3, and the length of the palladium bump is 11nm.
Performance test experiment of the crown gold-palladium nano heterogeneous material prepared in the embodiment 1:
1. photo-thermal capability test of crown gold-palladium nano heterogeneous material:
1) Taking 1 mL of coronal gold-palladium nano heterogeneous material (100 mug mL) -1 ) Fixing in a quartz cuvette;
2) With 808. 808nm laser at 0.75W cm -2 Is irradiated with the above solution for 10 minutes;
3) In the irradiation process, recording a temperature value every 30 seconds for drawing a photo-thermal curve;
2. photodynamic performance test of crown gold-palladium nano heterogeneous material:
1) mu.L of the crown gold palladium nano heterojunction material (100. Mu.g/mL) was mixed with 80. Mu.L of 2',7' -dichloro fluoroxantho diacetate (DCFH-DA, 29. Mu.M);
2) With 808. 808nm laser at 0.75W cm -2 Is irradiated with the above solution for 10 minutes;
3) After 24 hours of co-incubation, collecting fluorescence emission spectra of DCF within 500-600nm at excitation wavelength of 490 nm;
3. in vitro immunostimulation of dendritic cells by the coronary gold palladium nano heterojunction material itself:
1) Dendritic cells were isolated from bone marrow of approximately 8 week old BALB/c mice 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) The cultured dendritic cells were cultured at 1.6X10 5 Cell density of wells/cell density of wells was seeded in 6-well plates at 37 ℃ and 5% CO 2 Growing overnight in the atmosphere;
3) Removing the upper medium, adding 100 μg mL -1 Crown gold palladium nano heterojunction material and incubating 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 maturity of the DCs by a flow cytometer;
4. phototherapy in vitro immunostimulation of dendritic cells:
1) Bone marrow-derived dendritic cells isolated from BALB/c mice are inoculated into a Transwell lower cavity, and after co-incubation of a coronary gold-palladium nano heterojunction material and 4T1 cells, the dendritic cells are inoculated into an upper cavity;
2) With 808. 808nm laser at 0.75W cm -2 For 10 minutes;
3) After 6 hours of co-culture, cells were gently washed three times with PBS, DCs were stained with CD80, CD 86-labeled antibodies, and the maturity of DCs was measured by flow cytometry;
5. biocompatibility testing of the coronal gold-palladium nano heterogeneous material:
1) Mouse breast cancer cells 4T1 cells were 1X 10 4 Cell density of wells/cell density of wells was seeded into 96-well plates at 37 o C and 5% CO 2 Growing overnight in 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 was added -1 Crown gold palladium nano heterojunction material and incubating for 24 hours;
3) mu.L of 5 mg mL was added to each well -1 Incubating for 3.5 hours;
4) The cell culture medium was removed and 150. Mu.L of DMSO was added to each well. Then after shaking the plate for 10 minutes, the absorbance at 490 nm was measured to calculate cell activity;
6. killing experiment of crown gold-palladium nano heterogeneous material on tumor cells under 808nm laser irradiation:
1) Mouse breast cancer cells 4T1 cells were 1X 10 4 Cell density of wells/cell density of wells was seeded into 96-well plates at 37 o C and 5% CO 2 Growing overnight in 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 was added -1 Crown gold palladium nano heterojunction material and incubating for 6 hours;
3) After a continuous incubation time of 6 hours, the incubation time was reduced with 808nm laser (0.75W cm -2 ) The cells were irradiated for 10 minutes and incubated for an additional 18 hours;
4) mu.L of 5 mg mL was added to each well -1 Incubating for 3.5 hours;
5) The cell culture medium was removed and 150. Mu.L of 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.
FIG. 1 is a transmission electron micrograph of a crown gold-palladium nano heterogeneous material prepared in example 1. From FIG. 1, it is known that the diameter of the nano gold rod is 10.9nm, the aspect ratio is 3.6, and the length of the palladium bump is 11nm. The surface successfully synthesizes the crown gold-palladium nano heterogeneous material, and the size is uniform.
FIG. 2 is an absorption spectrum of the crown gold-palladium nano-heterogeneous material prepared in example 1, and it can be seen from FIG. 1 that the absorption peak of the crown gold-palladium nano-heterogeneous material is located near 808 nm.
FIG. 3 is a photo-thermal heating graph of the crown gold-palladium nano heterogeneous material prepared in example 1 under irradiation of 808nm near infrared light. As can be seen from fig. 3, under 808nm laser irradiation, the temperature is steadily increased, which indicates that the coronary gold-palladium nano heterogeneous material has good photo-thermal conversion performance.
FIG. 4 is a graph showing the generation of active oxygen radicals under irradiation of near infrared light at 808nm for the crown gold-palladium nano-heterogeneous material prepared in example 1. From fig. 4, it can be known that the coronary gold-palladium nano heterogeneous material can cause a significant increase of fluorescence intensity under the irradiation of near infrared light of 808nm, which indicates that active oxygen free radicals are generated efficiently, and the excellent photodynamic performance is shown.
FIG. 5 is a flow chart of data of the flow pattern of the dendritic cells, which is promoted by the nature of burrs carried by the gold-palladium nanoparticle heterogeneous material prepared in example 1, and the expression of costimulatory molecules (CD 80, CD 86) is a marker of DC maturation. The results demonstrate that the coronary gold-palladium nano-heterogeneous material itself is capable of inducing dendritic cell maturation, meaning that it has the potential to induce immune responses.
Fig. 6 is a schematic diagram (fig. 6A) and a flow chart (fig. 6B) of the maturation and activation of dendritic cells promoted by a large number of tumor-associated antigens generated after phototherapy by the coronal gold-palladium nano-heterogeneous material prepared in example 1. The results demonstrate that 4T1 cell debris can significantly enhance dendritic cell maturation after phototherapy.
Fig. 7 is a biosafety test chart of the coronal gold-palladium nano heterogeneous material prepared in example 1. The result shows that after the crown gold-palladium nano heterogeneous material is incubated for 24 hours together with 4T1 cells, the cell survival rate is over 80 percent, and the surface has good biocompatibility, so that the crown gold-palladium nano heterogeneous material can be used for in-vivo experiments of cells and organisms.
Fig. 8 is a graph for testing the killing ability of the crown gold-palladium nano heterogeneous material prepared in example 1 to tumor cells under the excitation of near infrared light. MTT result surface, the crown gold-palladium nanometer heterogeneous material presents the tumor cell killing capacity of concentration dependence under near infrared light excitation, which shows that the crown gold-palladium nanometer heterogeneous material prepared by the method can be used for killing tumor cells under near infrared light excitation condition.
Example 2
The preparation method of the coronary gold-palladium nano heterogeneous material comprises the following steps:
s1, adding cetyl pyridine chloride monohydrate into water, fully stirring and dissolving until the solution is in a transparent state, preparing cetyl pyridine chloride monohydrate solution with the concentration of 1mmol/L, and then 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 10mmol/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;
the nano gold rod is prepared by a seed-mediated growth method, and comprises the following steps:
s2-1, preparing a gold element seed solution:
adding 0.25mL of tetrachloroauric acid with the concentration of 10mmol/L into 5mL of cetyltrimethylammonium bromide solution with the concentration of 200mmol/L to prepare seed solution for later use;
s2-2, preparation of growth solution
(1) 3.08g of cetyltrimethylammonium chloride and 0.77g of sodium oleate are weighed and added into 250mL of water, and heated and dissolved until the solution is transparent;
(2) maintaining the heating temperature of the mixed solution in the step (1), adding 6mL of silver nitrate with the concentration of 4mmol/L and 250mL of tetrachloroauric acid with the concentration of 5mmol/L into the mixed solution, and stirring the mixed solution at the temperature of 30 ℃ for 150 minutes until the solution is colorless and transparent;
(3) adding 2mL of 37wt% hydrochloric acid solution into the colorless transparent solution prepared in the step (2), and stirring for 15 minutes;
(4) firstly, adding 0.6mL of sodium borohydride solution with the concentration of 10mmol/L into the seed solution prepared in the step S2-1 under intense stirring, and aging the obtained brown yellow solution at 30 ℃ for 30 minutes; meanwhile, adding 0.62mL of ascorbic acid solution with the concentration of 64mmol/L into the solution prepared in the step (3), and vigorously stirring for 30 seconds; finally, 0.4mL of the aged seed solution is quickly injected into the mixed solution, and the length-diameter ratio of the Au nano-rod is adjusted by adjusting the added content of the seed solution;
(5) stirring the solution prepared in the step (4) for 1 minute, and standing at 30 ℃ for overnight growth to prepare the nano gold rod.
S3, adding 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 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 with water for at least 3 times to prepare the crown-shaped gold-palladium nano heterostructure material.
In the crown gold-palladium nano heterogeneous material, the mass ratio of the gold element to the palladium element in the embodiment 2 is 1:0.1.
In the crown gold-palladium nano heterostructure material prepared in the embodiment 2, the mass ratio of gold element to palladium element is 1:0.1, and the length of the palladium bump is 5nm.
Fig. 9 is a transmission electron micrograph of the crown gold-palladium nano-heterogeneous material prepared in example 2, and it was observed that the crown gold-palladium nano-heterogeneous material was successfully prepared and the structure was uniform.
The coronary gold-palladium nano heterogeneous material prepared in the embodiment 2 has the photo-thermal, photodynamic and dendritic cell maturation stimulation capability prepared in the embodiment 1, and can also effectively kill tumor cells.
Example 3
The preparation method of the coronary gold-palladium nano heterogeneous material comprises the following steps:
s1, adding cetyl pyridine chloride monohydrate into water, fully stirring and dissolving until the solution is in a transparent state, preparing cetyl pyridine chloride monohydrate solution with the concentration of 1mmol/L, and then 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 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;
the nano gold rod is prepared by a seed-mediated growth method, and comprises the following steps:
s2-1, preparing a gold element seed solution:
adding 0.25mL of tetrachloroauric acid with the concentration of 10mmol/L into 5mL of cetyltrimethylammonium bromide solution with the concentration of 200mmol/L to prepare seed solution for later use;
s2-2, preparation of growth solution
(1) 3.08g of cetyltrimethylammonium chloride and 0.77g of sodium oleate are weighed and added into 250mL of water, and heated and dissolved until the solution is transparent;
(2) maintaining the heating temperature of the mixed solution in the step (1), adding 6mL of silver nitrate with the concentration of 4mmol/L and 250mL of tetrachloroauric acid with the concentration of 5mmol/L into the mixed solution, and stirring the mixed solution at the temperature of 30 ℃ for 150 minutes until the solution is colorless and transparent;
(3) adding 2mL of 37wt% hydrochloric acid solution into the colorless transparent solution prepared in the step (2), and stirring for 15 minutes;
(4) firstly, adding 0.6mL of sodium borohydride solution with the concentration of 10mmol/L into the seed solution prepared in the step S2-1 under intense stirring, and aging the obtained brown yellow solution at 30 ℃ for 30 minutes; meanwhile, adding 0.62mL of ascorbic acid solution with the concentration of 64mmol/L into the solution prepared in the step (3), and vigorously stirring for 30 seconds; finally, 0.4mL of the aged seed solution is quickly injected into the mixed solution, and the length-diameter ratio of the Au nano-rod is adjusted by adjusting the added content of the seed solution;
(5) stirring the solution prepared in the step (4) for 1 minute, and standing at 30 ℃ for overnight growth to prepare the nano gold rod.
S3, adding 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 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 with water for at least 3 times to prepare the crown-shaped gold-palladium nano heterostructure material.
In the crown gold-palladium nano heterogeneous material, the mass ratio of the gold element to the palladium element is 1:0.5 in the embodiment 3.
In the crown gold-palladium nano heterostructure material prepared in the embodiment 3, the mass ratio of gold element to palladium element is 1:0.5, and the length of the palladium bump is 13nm.
Fig. 10 is a transmission electron micrograph of the crown gold-palladium nano-heterogeneous material prepared in example 3, and it was observed that the crown gold-palladium nano-heterogeneous material was successfully prepared and the structure was uniform.
The coronary gold-palladium nano heterogeneous material prepared in the embodiment has the photo-thermal, photodynamic and dendritic cell maturation stimulation capability prepared in the embodiment 1, and can also effectively kill tumor cells.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present invention should be 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 claims.
Claims (7)
1. The application of a coronary gold-palladium nano heterogeneous material in preparing a medicament for killing in-situ tumor cells and inhibiting tumor recurrence and metastasis under the condition of near infrared light excitation is characterized in that: the existence form of gold element in the crown gold-palladium nano heterogeneous material is nano gold rod, the existence form of palladium element is bulge, and the palladium bulge grows on the outer surface of the nano gold rod irregularly, and the mass ratio of gold element to palladium element is 1 (0.1-0.5).
2. The use according to claim 1, characterized in that: 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 11nm.
3. The use according to claim 1, characterized in that: the mass ratio of the gold element to the palladium element is 1:0.3.
4. Use of the gold-palladium nanoparticle heterogeneous material according to claim 1 for the preparation of a medicament for killing in-situ tumor cells and inhibiting tumor recurrence and metastasis under near infrared excitation conditions, wherein the material comprises: the preparation method of the crown gold-palladium nano heterogeneous material comprises the following steps:
s1, adding cetyl pyridine chloride monohydrate into water, fully stirring and dissolving until the solution is in a transparent state, preparing cetyl pyridine chloride monohydrate solution with the concentration of 1-100mmol/L, and then 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 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 constant temperature of 65 ℃ for standing for 2 hours;
and S4, centrifuging the mixed solution prepared in the step S3 to obtain nano particles, and then washing the nano material with water for at least 3 times to obtain the crown gold-palladium nano heterostructure material.
5. The use according to claim 4, characterized in that:
in the step S2, the nano gold rod is prepared by a seed-mediated growth method, and comprises the following steps:
s2-1, preparing a gold element seed solution:
adding 0.25mL of tetrachloroauric acid with the concentration of 10mmol/L into 5mL of cetyltrimethylammonium bromide solution with the concentration of 200mmol/L to prepare seed solution for later use;
s2-2, preparation of growth solution
(1) 3.08g of cetyltrimethylammonium chloride and 0.77g of sodium oleate are weighed and added into 250mL of water, and heated and dissolved until the solution is transparent;
(2) maintaining the heating temperature of the mixed solution in the step (1), adding 6mL of silver nitrate with the concentration of 4mmol/L and 250mL of tetrachloroauric acid with the concentration of 5mmol/L into the mixed solution, and stirring the mixed solution at the temperature of 30 ℃ for 150 minutes until the solution is colorless and transparent;
(3) adding 2mL of 37wt% hydrochloric acid solution into the colorless transparent solution prepared in the step (2), and stirring for 15 minutes;
(4) firstly, adding 0.6mL of sodium borohydride solution with the concentration of 10mmol/L into the seed solution prepared in the step S2-1 under intense stirring, and aging the obtained brown yellow solution at 30 ℃ for 30 minutes; meanwhile, adding 0.62mL of ascorbic acid solution with the concentration of 64mmol/L into the solution prepared in the step (3), and vigorously stirring for 30 seconds; finally, 0.4-0.6 mL of the aged seed solution is quickly injected into the mixed solution;
(5) stirring the solution prepared in the step (4) for 1 minute, and standing at 30 ℃ for overnight growth to prepare the nano gold rod.
6. The use according to claim 5, characterized in that: in the step (4), the length-diameter ratio of the nano gold rod is adjusted by adjusting the added content of the seed solution.
7. The use according to claim 4, characterized in that: in the step S4, the centrifugal rotational speed was 7000rpm, and the centrifugal time was 10 minutes.
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