CN115137825A - Manganese-doped calcium phosphide-modified metal palladium nanoparticle and preparation method thereof - Google Patents
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Abstract
The invention discloses a manganese-doped calcium phosphide-modified metal palladium nanoparticle and a preparation method thereof. The manganese-doped calcium phosphide modified metal palladium nanoparticle with the photo-thermal conversion effect and the Fenton effect is prepared by using palladium acetylacetonate, polyvinylpyrrolidone, formaldehyde, a Tris-HCl solution containing calcium chloride and manganese chloride and a HEPES solution containing disodium hydrogen phosphate. The average particle size of the manganese-doped calcium phosphide-modified metal palladium nanoparticles is 80-250 nm, the preparation method is simple, and the manganese-doped calcium phosphide-modified metal palladium nanoparticles have good particle size distribution and biocompatibility. Under laser irradiation, the photo-thermal conversion efficiency and the photo-thermal stability are good; under the weak acidic condition, fenton or Fenton-like reaction can be carried out to generate hydroxyl free radicals, and glutathione in the tumor can be effectively consumed, so that the application of the glutathione in the tumor in photothermal therapy and chemokinetic therapy has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of medicines, and particularly relates to a manganese-doped calcium phosphide-modified metal palladium nanoparticle and a preparation method thereof.
Background
Cancer is one of the major diseases seriously threatening public health, and in recent years, the incidence and mortality of cancer have rapidly increased and become one of the major diseases threatening human health. The combined tumor therapy combines the advantages of various treatment methods, complements the disadvantages and plays an important role in treating tumors.
In recent years, photothermal therapy (PTT) based on near infrared light (NIR) for tumor treatment has attracted much attention. Photothermal therapy is a novel tumor treatment mode which utilizes photothermal materials with photothermal conversion efficiency to generate high temperature under the irradiation of near infrared light so as to kill cancer cells. Chemical kinetic therapy (CDT) utilizes transition metal ions to react with endogenous substances of tumor cells in Fenton or Fenton-like manner to generate Reactive Oxygen Species (ROS), thereby inducing apoptosis or necrosis of tumor cells, and certain metal ions (such as Mn) 2+ ) It can also be used as contrast agent for Magnetic Resonance Imaging (MRI). Optical treatment not only kills tumor cells by the photothermal effect of laser irradiation of photosensitizers, but also enhances the effect of other therapies such as CDT. At present, the photo-thermal materials based on iron, copper and the like are reported more in the metal photo-thermal materials, and the photo-thermal nano materials based on palladium-based metal are rarely used for anti-tumor treatment.
The currently reported palladium-based metal photo-thermal nano material, such as a two-dimensional metal palladium nano sheet, has excellent photo-thermal conversion efficiency, but still has the defects of complex preparation process, single function and the like. Therefore, palladium acetylacetonate, formaldehyde solution and polyvinylpyrrolidone are used for preparing palladium-based metal nanoparticles, biomineralization is carried out on the basis of the palladium-based metal nanoparticles, manganese-doped calcium phosphide is used for coating the metal palladium nanoparticles, and the average particle size of the metal palladium nanoparticles is 80-250 nm. Meanwhile, in a tumor subacid environment, the manganese-doped calcium phosphide coating can be subjected to pH responsive degradation to release metal palladium nanoparticles and Mn 2+ The metallic palladium nanoparticles can be reacted with H 2 O 2 Reaction to generate hydroxyl radical to kill tumor cells, mn 2+ It can also be used as contrast agent for Magnetic Resonance Imaging (MRI). Compared with the traditional single photothermal therapy or chemokinetic therapy, the manganese calcium phosphide modified metal palladium nanoparticle constructed by the method is expected to improve the treatment effect on tumors by combining photothermal therapy with chemokinetic therapy.
Disclosure of Invention
The invention aims to provide a manganese-doped calcium phosphide-modified metal palladium nanoparticle and a preparation method thereof, the prepared manganese-doped calcium phosphide-modified metal palladium nanoparticle has photo-thermal and chemical dynamic properties, and has the advantages of simple preparation process, good biocompatibility, uniform particle size distribution and glutathione consumption capability, thereby having wide application prospect in the field of tumor treatment.
In order to realize the purpose, the invention adopts the following technical scheme:
dissolving palladium acetylacetonate and polyvinylpyrrolidone in N, N-dimethylformamide, adding a formaldehyde solution after dissolving, transferring a reaction solution to a hydrothermal reaction kettle for reaction, adding acetone to precipitate nanoparticles, centrifuging, and washing with ethanol and ultrapure water for 2-3 times to obtain the metallic palladium nanoparticles. Adding a certain amount of calcium chloride and manganese chloride into the Tris-HCl buffer solution, and carrying out ultrasonic treatment until the calcium chloride and the manganese chloride are completely dissolved to obtain a Tris-HCl solution containing the calcium chloride and the manganese chloride; adding a certain amount of disodium hydrogen phosphate into HEPES buffer solution, carrying out ultrasonic treatment until the disodium hydrogen phosphate is completely dissolved to obtain HEPES solution containing disodium hydrogen phosphate, and mixing with the obtained Tris-HCl solution containing calcium chloride and manganese chloride to obtain a mixed solution. And adding the obtained metal palladium nanoparticles into the mixed solution, stirring for 4 hours at room temperature, centrifuging, and washing for 2-3 times by using ultrapure water to obtain the manganese-doped calcium phosphide-modified metal palladium nanoparticles. The method comprises the following specific steps:
(1) Dissolving 50-200 mg of palladium acetylacetonate in 10-30mL of N, N-dimethylformamide, respectively adding 160-480 mg of polyvinylpyrrolidone and 0.1-1 mL of formaldehyde solution, transferring the reaction solution into a reaction vessel after dissolving, reacting for 8-10 h at 100-120 ℃, adding 5mL of acetone to precipitate nanoparticles, centrifuging at the rotating speed of 8000-12000 rpm for 5-10 min, and respectively washing for 2-3 times by using ethanol-acetone mixed solution and ultrapure water to obtain metal palladium nanoparticles;
(2) Mixing Tris-HCl buffer solution containing 250-500 mM calcium chloride and 20-50 mM manganese chloride with HEPES buffer solution containing 6-50 mM disodium hydrogen phosphate to obtain mixed solution;
(3) Adding 1-10 mg of metal palladium nanoparticles into the mixed solution obtained in the step (2), stirring at room temperature for 4h, centrifuging at the rotating speed of 8000-12000 rpm for 5-10 min, and washing with ultrapure water for 2-3 times to obtain the manganese-doped calcium phosphide-modified metal palladium nanoparticles.
The innovation of the invention is that the palladium-based metal nanoparticle with the average particle size of 80-250 nm and excellent photothermal conversion effect is prepared by using palladium acetylacetonate, polyvinylpyrrolidone and formaldehyde solution for the first time by using a solvothermal method. It is then biomineralized to improve its biocompatibility and enhance its targeting. Compared with other metal nanoparticles, the manganese-doped calcium phosphide-modified metal palladium nanoparticle has the advantages of simple preparation process, good biocompatibility, acid-responsive degradation and glutathione consumption. Under laser irradiation, the manganese-doped calcium phosphide modified metal palladium nanoparticles can kill tumor cells through a photothermal conversion effect, and simultaneously release the metal palladium nanoparticles and Mn in response to a weak acidic condition of a tumor microenvironment 2+ The metallic palladium nanoparticles can be reacted with H 2 O 2 Reaction to generate hydroxyl radical to kill tumor cells, mn 2+ It can also be used as contrast agent for Magnetic Resonance Imaging (MRI). Compared with the traditional single photothermal therapy or chemokinetic therapy, the manganese calcium phosphide modified metal palladium nanoparticle constructed by the method is expected to improve the treatment effect on tumors by combining photothermal therapy with chemokinetic therapy.
Drawings
FIG. 1 is a diagram showing a particle size distribution of manganese-doped calcium phosphide-modified metal palladium nanoparticles;
FIG. 2 is an appearance diagram of a manganese-doped calcium phosphide-modified metal palladium nanoparticle suspension;
FIG. 3 is an in vitro photothermal graph of manganese-doped calcium phosphide-modified metallic palladium nanoparticles;
FIG. 4 is a diagram showing the detection result of hydroxyl radicals of manganese-doped calcium phosphide-modified metal palladium nanoparticles;
FIG. 5 is a graph showing the results of glutathione consumption assay of manganese-doped calcium phosphide-modified palladium nanoparticles;
FIG. 6 is a view of the biocompatibility of the metal palladium nanoparticle modified by manganese-doped calcium phosphide on normal cells;
FIG. 7 is a graph showing the tumor cell inhibitory effect of manganese-doped calcium phosphide-modified metal palladium nanoparticles;
Detailed Description
The present invention is further described in detail by the following examples, but the present invention is not limited to the following examples, and all equivalent modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
Example 1
The embodiment is a preparation method of a manganese-doped calcium phosphide-modified metal palladium nanoparticle, which comprises the following steps:
step (1): 50mg of palladium acetylacetonate was dissolved in 10mL of N, N-dimethylformamide, 160mg of polyvinylpyrrolidone and 1mL of formaldehyde solution were added, and after dissolution, the reaction mixture was transferred to a reaction vessel and reacted at 100 ℃ for 8 hours. Adding 5mL of acetone to precipitate the nanoparticles, centrifuging at 12000rpm for 5min, and washing with ethanol-acetone mixed solution and ultrapure water for 2-3 times to obtain the metal palladium nanoparticles.
Step (2): mixing 10mM Tris-HCl buffer containing 250mM calcium chloride and 20mM manganese chloride and 10mM HEPES buffer containing 6mM disodium hydrogen phosphate according to a volume ratio of 1:1, mixing uniformly.
And (3): and (3) adding 10mg of metal palladium nanoparticles into the mixed solution obtained in the step (2), and stirring at room temperature for 4 hours. Centrifuging at the rotating speed of 10000rpm for 5min, and washing for 2-3 times by using ultrapure water to obtain the manganese-doped calcium phosphide-modified metal palladium nanoparticle.
Example 2
The embodiment is a preparation method of a manganese-doped calcium phosphide-modified metal palladium nanoparticle, which comprises the following steps:
step (1): 50mg of palladium acetylacetonate was dissolved in 10mL of N, N-dimethylformamide, and then 160mg of polyvinylpyrrolidone and 0.5mL of formaldehyde solution were added, respectively, and after dissolution, the reaction solution was transferred to a reaction vessel and reacted at 100 ℃ for 8 hours. Adding 5mL of acetone to precipitate the nanoparticles, centrifuging at 12000rpm for 5min, and washing with ethanol-acetone mixed solution and ultrapure water for 2-3 times to obtain the metal palladium nanoparticles.
Step (2): mixing 10mM Tris-HCl buffer containing 250mM calcium chloride and 20mM manganese chloride and 10mM HEPES buffer containing 6mM disodium hydrogen phosphate according to a volume ratio of 1:1 and mixing uniformly.
And (3): and (3) adding 10mg of metal palladium nanoparticles into the mixed solution obtained in the step (2), and stirring at room temperature for 4 hours. Centrifuging at 10000rpm for 5min, and washing with ultrapure water for 2-3 times to obtain the manganese-doped calcium phosphide-modified metal palladium nanoparticle.
Example 3
The embodiment is a preparation method of manganese-doped calcium phosphide-modified metal palladium nanoparticles, which comprises the following steps:
step (1): 50mg of palladium acetylacetonate was dissolved in 10mL of N, N-dimethylformamide, and then 160mg of polyvinylpyrrolidone and 0.1mL of a formaldehyde solution were added, respectively, and after dissolution, the reaction mixture was transferred to a reaction vessel and reacted at 100 ℃ for 8 hours. Adding 5mL of acetone to precipitate the nanoparticles, centrifuging at 12000rpm for 5min, and washing with ethanol-acetone mixed solution and ultrapure water for 2-3 times to obtain the metal palladium nanoparticles.
Step (2): mixing 10mM Tris-HCl buffer containing 250mM calcium chloride and 20mM manganese chloride and 10mM HEPES buffer containing 6mM disodium hydrogen phosphate according to a volume ratio of 1:1, mixing uniformly.
And (3): and (3) adding 10mg of metal palladium nanoparticles into the mixed solution obtained in the step (2), and stirring at room temperature for 4 hours. Centrifuging at 10000rpm for 5min, and washing with ultrapure water for 2-3 times to obtain the manganese-doped calcium phosphide-modified metal palladium nanoparticle.
Example 4
The embodiment is a preparation method of a manganese-doped calcium phosphide-modified metal palladium nanoparticle, which comprises the following steps:
step (1): 50mg of palladium acetylacetonate was dissolved in 10mL of N, N-dimethylformamide, and then 160mg of polyvinylpyrrolidone and 0.1mL of formaldehyde solution were added, respectively, and after dissolution, the reaction solution was transferred to a reaction vessel and reacted at 100 ℃ for 10 hours. Adding 5mL of acetone to precipitate the nanoparticles, centrifuging at 12000rpm for 5min, and washing with ethanol-acetone mixed solution and ultrapure water for 2-3 times to obtain the metal palladium nanoparticles.
Step (2): mixing 10mM Tris-HCl buffer containing 250mM calcium chloride and 20mM manganese chloride and 10mM HEPES buffer containing 6mM disodium hydrogen phosphate according to a volume ratio of 1:1, mixing uniformly.
And (3): and (3) adding 10mg of metal palladium nanoparticles into the mixed solution obtained in the step (2), and stirring at room temperature for 4 hours. Centrifuging at 10000rpm for 5min, and washing with ultrapure water for 2-3 times to obtain the manganese-doped calcium phosphide-modified metal palladium nanoparticle.
Example 5
The embodiment is a preparation method of a manganese-doped calcium phosphide-modified metal palladium nanoparticle, which comprises the following steps:
step (1): 100mg of palladium acetylacetonate was dissolved in 10mL of N, N-dimethylformamide, and then 160mg of polyvinylpyrrolidone and 0.1mL of a formaldehyde solution were added, respectively, and after dissolution, the reaction mixture was transferred to a reaction vessel and reacted at 100 ℃ for 8 hours. Adding 5mL of acetone to precipitate the nanoparticles, centrifuging at 12000rpm for 5min, and washing with ethanol-acetone mixed solution and ultrapure water for 2-3 times to obtain the metal palladium nanoparticles.
Step (2): mixing 10mM Tris-HCl buffer containing 250mM calcium chloride and 20mM manganese chloride and 10mM HEPES buffer containing 6mM disodium hydrogen phosphate according to a volume ratio of 1:1, mixing uniformly.
And (3): and (3) adding 10mg of metal palladium nanoparticles into the mixed solution obtained in the step (2), and stirring at room temperature for 4 hours. Centrifuging at the rotating speed of 10000rpm for 5min, and washing for 2-3 times by using ultrapure water to obtain the manganese-doped calcium phosphide-modified metal palladium nanoparticle.
Example 6
The embodiment is a preparation method of a manganese-doped calcium phosphide-modified metal palladium nanoparticle, which comprises the following steps:
step (1): 50mg of palladium acetylacetonate was dissolved in 30mL of N, N-dimethylformamide, 160mg of polyvinylpyrrolidone and 0.1mL of a formaldehyde solution were added, respectively, and after dissolution, the reaction mixture was transferred to a reaction vessel and reacted at 100 ℃ for 8 hours. Adding 5mL of acetone to precipitate the nanoparticles, centrifuging at 12000rpm for 5min, and washing with ethanol-acetone mixed solution and ultrapure water for 2-3 times to obtain the metal palladium nanoparticles.
Step (2): mixing 10mM Tris-HCl buffer containing 250mM calcium chloride and 20mM manganese chloride and 10mM HEPES buffer containing 6mM disodium hydrogen phosphate according to a volume ratio of 1:1, mixing uniformly.
And (3): and (3) adding 10mg of metal palladium nanoparticles into the mixed solution obtained in the step (2), and stirring at room temperature for 4 hours. Centrifuging at the rotating speed of 10000rpm for 5min, and washing for 2-3 times by using ultrapure water to obtain the manganese-doped calcium phosphide-modified metal palladium nanoparticle.
Example 7
The embodiment is a preparation method of a manganese-doped calcium phosphide-modified metal palladium nanoparticle, which comprises the following steps:
step (1): 50mg of palladium acetylacetonate was dissolved in 10mL of N, N-dimethylformamide, 480mg of polyvinylpyrrolidone and 0.1mL of formaldehyde solution were added, and after dissolution, the reaction mixture was transferred to a reaction vessel and reacted at 100 ℃ for 8 hours. Adding 5mL of acetone to precipitate the nanoparticles, centrifuging at 12000rpm for 5min, and washing with ethanol-acetone mixed solution and ultrapure water for 2-3 times to obtain the metal palladium nanoparticles.
Step (2): mixing 10mM Tris-HCl buffer containing 250mM calcium chloride and 20mM manganese chloride and 10mM HEPES buffer containing 6mM disodium hydrogen phosphate according to a volume ratio of 1:1, mixing uniformly.
And (3): and (3) adding 10mg of metal palladium nanoparticles into the mixed solution obtained in the step (2), and stirring at room temperature for 4 hours. Centrifuging at 10000rpm for 5min, and washing with ultrapure water for 2-3 times to obtain the manganese-doped calcium phosphide-modified metal palladium nanoparticle.
Example 8
The embodiment is a preparation method of a manganese-doped calcium phosphide-modified metal palladium nanoparticle, which comprises the following steps:
step (1): 50mg of palladium acetylacetonate was dissolved in 10mL of N, N-dimethylformamide, and then 160mg of polyvinylpyrrolidone and 0.1mL of a formaldehyde solution were added, respectively, and after dissolution, the reaction mixture was transferred to a reaction vessel and reacted at 100 ℃ for 8 hours. Adding 5mL of acetone to precipitate the nanoparticles, centrifuging at 12000rpm for 5min, and washing with ethanol-acetone mixed solution and ultrapure water for 2-3 times to obtain the metal palladium nanoparticles.
Step (2): mixing 10mM Tris-HCl buffer containing 25mM calcium chloride and 10mM manganese chloride and 10mM HEPES buffer containing 6mM disodium hydrogen phosphate according to a volume ratio of 1:1, mixing uniformly.
And (3): and (3) adding 10mg of metal palladium nanoparticles into the mixed solution obtained in the step (2), and stirring at room temperature for 4 hours. Centrifuging at 10000rpm for 5min, and washing with ultrapure water for 2-3 times to obtain the manganese-doped calcium phosphide-modified metal palladium nanoparticle.
Example 9
The embodiment is a preparation method of manganese-doped calcium phosphide-modified metal palladium nanoparticles, which comprises the following steps:
step (1): 50mg of palladium acetylacetonate was dissolved in 10mL of N, N-dimethylformamide, and then 160mg of polyvinylpyrrolidone and 0.1mL of formaldehyde solution were added, respectively, and after dissolution, the reaction solution was transferred to a reaction vessel and reacted at 100 ℃ for 8 hours. Adding 5mL of acetone to precipitate the nanoparticles, centrifuging at 12000rpm for 5min, and washing with ethanol-acetone mixed solution and ultrapure water for 2-3 times to obtain the metal palladium nanoparticles.
Step (2): mixing 10mM Tris-HCl buffer containing 250mM calcium chloride and 20mM manganese chloride and 10mM HEPES buffer containing 20mM disodium hydrogen phosphate according to a volume ratio of 1:1 and mixing uniformly.
And (3): and (3) adding 10mg of metal palladium nanoparticles into the mixed solution obtained in the step (2), and stirring at room temperature for 4 hours. Centrifuging at 10000rpm for 5min, and washing with ultrapure water for 2-3 times to obtain the manganese-doped calcium phosphide-modified metal palladium nanoparticle.
Example 10
The embodiment is a preparation method of manganese-doped calcium phosphide-modified metal palladium nanoparticles, which comprises the following steps:
step (1): 50mg of palladium acetylacetonate was dissolved in 10mL of N, N-dimethylformamide, and then 160mg of polyvinylpyrrolidone and 0.1mL of a formaldehyde solution were added, respectively, and after dissolution, the reaction mixture was transferred to a reaction vessel and reacted at 100 ℃ for 8 hours. Adding 5mL of acetone to precipitate the nanoparticles, centrifuging at 12000rpm for 5min, and washing with an ethanol-acetone mixed solution and ultrapure water for 2-3 times to obtain the metal palladium nanoparticles.
Step (2): mixing 10mM Tris-HCl buffer containing 250mM calcium chloride and 20mM manganese chloride and 10mM HEPES buffer containing 6mM disodium hydrogen phosphate according to a volume ratio of 1:1 and mixing uniformly.
And (3): and (3) adding 5mg of metal palladium nanoparticles into the mixed solution obtained in the step (2), and stirring at room temperature for 4 hours. Centrifuging at the rotating speed of 10000rpm for 5min, and washing for 2-3 times by using ultrapure water to obtain the manganese-doped calcium phosphide-modified metal palladium nanoparticle.
Example 11
The particle size distribution result of the manganese-doped calcium phosphide-modified metal palladium nanoparticle is shown in figure 1; the appearance of the suspension is shown in figure 2. As can be seen from the figure, the manganese-doped calcium phosphide-modified metal palladium nanoparticles have small particle size and uniform distribution, and the average particle size is about 119.6 nm.
Example 12
The power density is 1.0W/cm 2 Irradiating the manganese-doped calcium phosphide-modified metal palladium nanoparticle suspension by using laser at 808nm, and recording the temperature change within 10 minutes of irradiation. The result is shown in fig. 3, the temperature of the manganese-doped calcium phosphide-modified metal palladium nanoparticle suspension gradually rises along with the increase of the laser irradiation time, and the nanoparticles have good photothermal conversion performance.
Example 13
The generation of hydroxyl radicals after the reaction of the manganese-doped calcium phosphide-modified metal palladium nanoparticles for 5min under the conditions of pH7.4, pH6.5 and pH6.0 is detected by adopting a 3,3', 5' -tetramethylbenzidine method. As shown in fig. 4, the manganese-doped calcium phosphide-modified metal palladium nanoparticle can generate more hydroxyl radicals under the condition of ph6.0, which indicates that the nanoparticle can perform fenton reaction and has a certain acid responsiveness.
Example 14
The ability of the manganese-doped calcium phosphide-modified metal palladium nanoparticle to consume glutathione under the condition of pH6.5 is detected by adopting a 5,5' -dithiobis (2-nitrobenzoic acid) method. As shown in fig. 5, the glutathione content gradually decreases with time under weakly acidic conditions, indicating that the manganese-doped calcium phosphide-modified palladium nanoparticle is expected to realize glutathione depletion therapy when used for antitumor therapy.
Example 15
The biocompatibility of the manganese-doped calcium phosphide-modified metal palladium nanoparticle on human umbilical vein endothelial cells HUVEC is detected by adopting an MTT method. Taking HUVEC cells in logarithmic growth phase, adjusting cell density to 7000 cells/well with DMEM medium containing 10% fetal bovine serum, inoculating into 96-well plate, and making CO 5% at 37 deg.C 2 The culture was carried out overnight in an incubator. The blank group is a culture medium without drugs, the control group is 4T1 cell fluid which is normally cultured without drugs, the experimental group is a culture medium containing manganese-doped calcium phosphide-modified metal palladium nanoparticles with different concentrations, each group has 6 multiple holes, the supernatant is discarded after the continuous culture for 24 hours, the cells are washed for 3 times by sterile PBS buffer solution, 100 mu L of serum-free culture medium containing MTT is added again, and the cells are incubated for 4 hours in a dark place. The supernatant was aspirated, 150. Mu.L of DMSO solution was added to each well, shaken for 10 minutes, and the absorbance at a wavelength of 490nm was measured with a microplate reader, and the cell viability was calculated. As shown in FIG. 6, the results show that the manganese-doped calcium phosphide-modified metal palladium nanoparticles have good safety.
Example 16
The cytotoxicity of the manganese-doped calcium phosphide-modified metal palladium nanoparticles on breast cancer cells 4T1 is detected by adopting an MTT method. Taking 4T1 cells in logarithmic growth phase, adjusting cell density to 7000 cells/well with 1640 medium containing 10% fetal bovine serum, inoculating in 96-well plate, and making 5% CO at 37 deg.C 2 The culture was carried out overnight in an incubator. Blank group isThe culture medium containing medicine, the control group is 4T1 cell sap cultured normally without medicine, the experimental group is culture medium containing manganese-doped calcium phosphide-modified metal palladium nanoparticles with different concentrations, each group has 6 multiple holes, and the experimental group is given 1.0W/cm after continuously culturing for 12h 2 Laser irradiation was performed for 5 minutes. After 24h the supernatant was discarded and washed 3 times with sterile PBS buffer, 100 μ L of serum free medium containing MTT was added again and incubated for 4h protected from light. The supernatant was aspirated, 150. Mu.L of DMSO solution was added to each well, shaken for 10 minutes, and the absorbance at a wavelength of 490nm was measured with a microplate reader, and the cell viability was calculated. As shown in fig. 7, the results indicate that the manganese-doped calcium phosphide-modified metal palladium nanoparticles after laser irradiation have a significant inhibitory effect on 4T1 tumor cells.
Claims (4)
1. The manganese-doped calcium phosphide-modified metal palladium nanoparticle is characterized in that the manganese-doped calcium phosphide-modified metal palladium nanoparticle is prepared from palladium acetylacetonate, polyvinylpyrrolidone, formaldehyde, a Tris-HCl solution containing calcium chloride and manganese chloride and a HEPES solution containing disodium hydrogen phosphate;
the manganese-doped calcium phosphide-modified metal palladium nanoparticle is prepared by the following preparation method:
(1) Dissolving palladium acetylacetonate and polyvinylpyrrolidone in N, N-dimethylformamide, adding a formaldehyde solution, transferring the reaction solution to a hydrothermal reaction kettle for reaction, centrifuging and washing to obtain metal palladium nanoparticles;
(2) Mixing a Tris-HCl solution containing a certain amount of calcium chloride and manganese chloride with a HEPES solution containing disodium hydrogen phosphate to obtain a mixed solution;
(3) And (3) adding the metal palladium nanoparticles obtained in the step (1) into the mixed solution obtained in the step (2), stirring, centrifuging and washing to obtain the manganese-doped calcium phosphide-modified metal palladium nanoparticles.
2. The manganese-doped calcium phosphide-modified metal palladium nanoparticle as claimed in claim 1, wherein the preparation method specifically comprises:
(1) Dissolving 50-200 mg of palladium acetylacetonate in 10-30mL of N, N-dimethylformamide, respectively adding 160-480 mg of polyvinylpyrrolidone and 0.1-1 mL of formaldehyde solution, transferring the reaction solution into a reaction vessel after dissolving, reacting for 8-10 h at 100-120 ℃, adding acetone to precipitate nanoparticles, centrifuging at the rotating speed of 8000-12000 rpm for 5-10 min, and respectively washing for 2-3 times by using ethanol-acetone mixed solution and ultrapure water to obtain metal palladium nanoparticles;
(2) Mixing Tris-HCl buffer solution containing 250-500 mM calcium chloride and 20-50 mM manganese chloride with HEPES buffer solution containing 6-50 mM disodium hydrogen phosphate to obtain mixed solution;
(3) And (3) adding 1-10 mg of metal palladium nanoparticles obtained in the step (1) into 1-10 mL of mixed solution obtained in the step (2), stirring, centrifuging and washing to obtain the manganese-doped calcium phosphide-modified metal palladium nanoparticles.
3. The manganese-doped calcium phosphide-modified metal palladium nanoparticle as claimed in claims 1 and 2, wherein the average particle size of the manganese-doped calcium phosphide-modified metal palladium nanoparticle is 80-250 nm.
4. The manganese-doped calcium phosphide-modified metallic palladium nanoparticle as claimed in claims 1 and 2, wherein the manganese-doped calcium phosphide-modified metallic palladium nanoparticle can be used for combined chemokinetic treatment of tumor photothermal therapy.
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