CN115137825B - Manganese-doped calcium phosphide-modified metal palladium nanoparticle and preparation method thereof - Google Patents
Manganese-doped calcium phosphide-modified metal palladium nanoparticle and preparation method thereof Download PDFInfo
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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 photothermal conversion effect and the Fenton effect is prepared by using palladium acetylacetonate, polyvinylpyrrolidone, formaldehyde, tris-HCl solution containing calcium chloride and manganese chloride and HEPES solution containing disodium hydrogen phosphate. The average particle size of the manganese-doped calcium phosphide modified metal palladium nanoparticle is 80-250 nm, and the preparation method is simple and has good particle size distribution and biocompatibility. Under the irradiation of laser, the light-heat conversion efficiency and the light-heat stability are good; under the weak acidic condition, fenton or Fenton-like reaction can be generated to generate hydroxyl free radicals, and glutathione in tumors can be effectively consumed, so that the application of the compound has a wide application prospect in the photo-thermal treatment and chemical kinetics treatment of tumors.
Description
Technical Field
The invention belongs to the technical field of medicines, and particularly relates to manganese-doped calcium phosphide-modified metal palladium nanoparticles and a preparation method thereof.
Background
Cancer is one of the major diseases severely threatening public health, and in recent years, the incidence and mortality rate of cancer have rapidly increased, and has become one of the major diseases threatening human health. The combination therapy of tumors combines the advantages of various therapeutic methods, complements the disadvantages thereof, and plays an important role in tumor treatment.
In recent years, the use of near infrared light (NIR) based photothermal therapy (PTT) for tumor treatment has attracted widespread attention. Photothermal therapy is a novel tumor treatment mode which utilizes a photothermal material with photothermal conversion efficiency to generate high temperature under the irradiation of near infrared light so as to kill cancer cells. Chemical Dynamic Therapy (CDT) uses the Fenton or Fenton-like reaction of transition metal ions with substances endogenous to tumor cells to generate Reactive Oxygen Species (ROS) to induce apoptosis or necrosis of tumor cells, and at the same time, certain metal ions (such as Mn 2+ ) But also as a Magnetic Resonance Imaging (MRI) contrast agent. Optical treatment not only kills tumor cells by photothermal effects generated by laser irradiation of photosensitizers, but also enhances the efficacy of other therapies such as CDT. At present, a lot of photothermal materials based on iron, copper and the like are reported in metal photothermal materials, but few photothermal nanomaterials based on palladium-based metals are reported for anti-tumor treatment.
The 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, and manganese-doped calcium phosphide is used for coating the metal palladium nanoparticles, wherein the average particle size of the metal palladium nanoparticles is 80-250 nm. Meanwhile, in the slightly acidic environment of tumors, the manganese-doped calcium phosphide coating can undergo pH responsive degradation to release metal palladium nanoparticles and Mn 2+ The metal palladium nanoparticle can be combined with H 2 O 2 Reaction to generate hydroxyl radical to kill tumor cells, mn 2+ But also as a Magnetic Resonance Imaging (MRI) contrast agent. Compared with the traditional single photothermal therapy or chemical kinetics therapy, the manganese-calcium phosphide modified metal palladium nanoparticle constructed at the time is hopeful to improve the treatment effect on tumors by combining photothermal therapy with chemical kinetics therapy.
Disclosure of Invention
The invention aims to provide manganese-doped calcium phosphide-modified metal palladium nanoparticles and a preparation method thereof, and the prepared manganese-doped calcium phosphide-modified metal palladium nanoparticles have photo-thermal and chemical kinetics performances, and are simple in preparation process, good in biocompatibility, uniform in particle size distribution and capable of consuming glutathione, so that the manganese-doped calcium phosphide-modified metal palladium nanoparticles have a wide application prospect in the field of tumor treatment.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
dissolving palladium acetylacetonate and polyvinylpyrrolidone in N, N-dimethylformamide, adding formaldehyde solution after dissolving, transferring the reaction solution into 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 metal palladium nanoparticles. Adding a certain amount of calcium chloride and manganese chloride into Tris-HCl buffer solution, and performing 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 the HEPES buffer solution, carrying out ultrasonic treatment until the disodium hydrogen phosphate is completely dissolved to obtain a HEPES solution containing the disodium hydrogen phosphate, and mixing the HEPES solution with the obtained Tris-HCl solution containing calcium chloride and manganese chloride to obtain a mixed solution. And adding the obtained metal palladium nano particles 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 nano particles. The method comprises the following specific steps:
(1) Dissolving 50-200 mg of palladium acetylacetonate in 10-30 mL 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 8000-12000 rpm for 5-10 min, and washing with ethanol-acetone mixed solution and ultrapure water for 2-3 times 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 nano particles into the mixed solution in the step (2), stirring for 4 hours at room temperature, centrifuging at 8000-12000 rpm for 5-10 min, and washing for 2-3 times by using ultrapure water to obtain the manganese-doped calcium phosphide modified metal palladium nano particles.
The innovation of the invention is that palladium acetylacetonate, polyvinylpyrrolidone and formaldehyde solution are used for the first time by using a solvothermal method to prepare the palladium-based metal nanoparticle with the average particle size of 80-250 nm and excellent photo-thermal conversion effect. 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 the irradiation of laser, the manganese-doped calcium phosphide-modified metal palladium nanoparticle can kill tumor cells through the photo-thermal conversion effect, and simultaneously release the metal palladium nanoparticle and Mn in response to the weak acidic condition of tumor microenvironment 2+ The metal palladium nanoparticle can be combined with H 2 O 2 Reaction to generate hydroxyl radical to kill tumor cells, mn 2+ But also as a Magnetic Resonance Imaging (MRI) contrast agent. Compared with the traditional single photothermal therapy or chemical kinetics therapy, the manganese-calcium phosphide modified metal palladium nanoparticle constructed at the time is hopeful to improve the treatment effect on tumors by combining photothermal therapy with chemical kinetics therapy.
Drawings
FIG. 1 is a graph showing the particle size distribution of manganese-doped calcium phosphide-modified metallic palladium nanoparticles;
FIG. 2 is an external view of a manganese-doped calcium phosphide-modified metallic palladium nanoparticle suspension;
FIG. 3 is an in vitro photothermogram of manganese doped calcium phosphide-modified metallic palladium nanoparticles;
FIG. 4 is a graph of the hydroxyl radical detection results of manganese-doped calcium phosphide-modified metallic palladium nanoparticles;
FIG. 5 is a graph of the glutathione consumption capability detection result of manganese-doped calcium phosphide-modified metallic palladium nanoparticles;
FIG. 6 is a view for examining the biocompatibility of manganese-doped calcium phosphide-modified metallic palladium nanoparticles against normal cells;
FIG. 7 is a graph showing the inhibition of tumor cells by Mn-doped calcium phosphide-modified metallic palladium nanoparticles;
Detailed Description
The present invention will be 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 construed to be included in the scope of the present invention.
Example 1
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 160mg of polyvinylpyrrolidone and 1mL of formaldehyde solution were added thereto, respectively, and the reaction mixture was transferred to a reaction vessel and reacted at 100℃for 8 hours. Adding 5mL of acetone to precipitate nano particles, centrifuging at 12000rpm for 5min, and then washing with ethanol-acetone mixed solution and ultrapure water for 2-3 times to obtain metal palladium nano particles.
Step (2): 10mM Tris-HCl buffer containing 250mM calcium chloride and 20mM manganese chloride and 10mM HEPES buffer containing 6mM disodium hydrogen phosphate were mixed in a volume ratio of 1:1, mixing uniformly.
Step (3): 10mg of metallic palladium nanoparticles was added to the mixed solution obtained in the step (2), and stirred at room temperature for 4 hours. Centrifuging at 10000rpm for 5min, and washing with ultrapure water for 2-3 times to obtain Mn-doped calcium phosphide modified metal palladium nanoparticle.
Example 2
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 160mg of polyvinylpyrrolidone and 0.5mL of formaldehyde solution were added thereto, respectively, and the reaction mixture was transferred to a reaction vessel and reacted at 100℃for 8 hours. Adding 5mL of acetone to precipitate nano particles, centrifuging at 12000rpm for 5min, and then washing with ethanol-acetone mixed solution and ultrapure water for 2-3 times to obtain metal palladium nano particles.
Step (2): 10mM Tris-HCl buffer containing 250mM calcium chloride and 20mM manganese chloride and 10mM HEPES buffer containing 6mM disodium hydrogen phosphate were mixed in a volume ratio of 1:1, mixing uniformly.
Step (3): 10mg of metallic palladium nanoparticles was added to the mixed solution obtained in the step (2), and stirred at room temperature for 4 hours. Centrifuging at 10000rpm for 5min, and washing with ultrapure water for 2-3 times to obtain Mn-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 160mg of polyvinylpyrrolidone and 0.1mL of formaldehyde solution were added thereto, respectively, and the reaction mixture was transferred to a reaction vessel and reacted at 100℃for 8 hours. Adding 5mL of acetone to precipitate nano particles, centrifuging at 12000rpm for 5min, and then washing with ethanol-acetone mixed solution and ultrapure water for 2-3 times to obtain metal palladium nano particles.
Step (2): 10mM Tris-HCl buffer containing 250mM calcium chloride and 20mM manganese chloride and 10mM HEPES buffer containing 6mM disodium hydrogen phosphate were mixed in a volume ratio of 1:1, mixing uniformly.
Step (3): 10mg of metallic palladium nanoparticles was added to the mixed solution obtained in the step (2), and stirred at room temperature for 4 hours. Centrifuging at 10000rpm for 5min, and washing with ultrapure water for 2-3 times to obtain Mn-doped calcium phosphide modified metal palladium nanoparticle.
Example 4
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 160mg of polyvinylpyrrolidone and 0.1mL of formaldehyde solution were added thereto, respectively, and the reaction mixture was transferred to a reaction vessel and reacted at 100℃for 10 hours. Adding 5mL of acetone to precipitate nano particles, centrifuging at 12000rpm for 5min, and then washing with ethanol-acetone mixed solution and ultrapure water for 2-3 times to obtain metal palladium nano particles.
Step (2): 10mM Tris-HCl buffer containing 250mM calcium chloride and 20mM manganese chloride and 10mM HEPES buffer containing 6mM disodium hydrogen phosphate were mixed in a volume ratio of 1:1, mixing uniformly.
Step (3): 10mg of metallic palladium nanoparticles was added to the mixed solution obtained in the step (2), and stirred at room temperature for 4 hours. Centrifuging at 10000rpm for 5min, and washing with ultrapure water for 2-3 times to obtain Mn-doped calcium phosphide modified metal palladium nanoparticle.
Example 5
The embodiment is a preparation method of manganese-doped calcium phosphide-modified metal palladium nanoparticles, which comprises the following steps:
step (1): 100mg of palladium acetylacetonate was dissolved in 10mL of N, N-dimethylformamide, and 160mg of polyvinylpyrrolidone and 0.1mL of formaldehyde solution were added thereto, respectively, and the reaction mixture was transferred to a reaction vessel and reacted at 100℃for 8 hours. Adding 5mL of acetone to precipitate nano particles, centrifuging at 12000rpm for 5min, and then washing with ethanol-acetone mixed solution and ultrapure water for 2-3 times to obtain metal palladium nano particles.
Step (2): 10mM Tris-HCl buffer containing 250mM calcium chloride and 20mM manganese chloride and 10mM HEPES buffer containing 6mM disodium hydrogen phosphate were mixed in a volume ratio of 1:1, mixing uniformly.
Step (3): 10mg of metallic palladium nanoparticles was added to the mixed solution obtained in the step (2), and stirred at room temperature for 4 hours. Centrifuging at 10000rpm for 5min, and washing with ultrapure water for 2-3 times to obtain Mn-doped calcium phosphide modified metal palladium nanoparticle.
Example 6
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 30mL of N, N-dimethylformamide, and 160mg of polyvinylpyrrolidone and 0.1mL of formaldehyde solution were added thereto, respectively, and the reaction mixture was transferred to a reaction vessel and reacted at 100℃for 8 hours. Adding 5mL of acetone to precipitate nano particles, centrifuging at 12000rpm for 5min, and then washing with ethanol-acetone mixed solution and ultrapure water for 2-3 times to obtain metal palladium nano particles.
Step (2): 10mM Tris-HCl buffer containing 250mM calcium chloride and 20mM manganese chloride and 10mM HEPES buffer containing 6mM disodium hydrogen phosphate were mixed in a volume ratio of 1:1, mixing uniformly.
Step (3): 10mg of metallic palladium nanoparticles was added to the mixed solution obtained in the step (2), and stirred at room temperature for 4 hours. Centrifuging at 10000rpm for 5min, and washing with ultrapure water for 2-3 times to obtain Mn-doped calcium phosphide modified metal palladium nanoparticle.
Example 7
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, 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 nano particles, centrifuging at 12000rpm for 5min, and then washing with ethanol-acetone mixed solution and ultrapure water for 2-3 times to obtain metal palladium nano particles.
Step (2): 10mM Tris-HCl buffer containing 250mM calcium chloride and 20mM manganese chloride and 10mM HEPES buffer containing 6mM disodium hydrogen phosphate were mixed in a volume ratio of 1:1, mixing uniformly.
Step (3): 10mg of metallic palladium nanoparticles was added to the mixed solution obtained in the step (2), and stirred at room temperature for 4 hours. Centrifuging at 10000rpm for 5min, and washing with ultrapure water for 2-3 times to obtain Mn-doped calcium phosphide modified metal palladium nanoparticle.
Example 8
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 160mg of polyvinylpyrrolidone and 0.1mL of formaldehyde solution were added thereto, respectively, and the reaction mixture was transferred to a reaction vessel and reacted at 100℃for 8 hours. Adding 5mL of acetone to precipitate nano particles, centrifuging at 12000rpm for 5min, and then washing with ethanol-acetone mixed solution and ultrapure water for 2-3 times to obtain metal palladium nano particles.
Step (2): 10mM Tris-HCl buffer containing 25mM calcium chloride and 10mM manganese chloride and 10mM HEPES buffer containing 6mM disodium hydrogen phosphate were mixed in a volume ratio of 1:1, mixing uniformly.
Step (3): 10mg of metallic palladium nanoparticles was added to the mixed solution obtained in the step (2), and stirred at room temperature for 4 hours. Centrifuging at 10000rpm for 5min, and washing with ultrapure water for 2-3 times to obtain Mn-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 160mg of polyvinylpyrrolidone and 0.1mL of formaldehyde solution were added thereto, respectively, and the reaction mixture was transferred to a reaction vessel and reacted at 100℃for 8 hours. Adding 5mL of acetone to precipitate nano particles, centrifuging at 12000rpm for 5min, and then washing with ethanol-acetone mixed solution and ultrapure water for 2-3 times to obtain metal palladium nano particles.
Step (2): 10mM Tris-HCl buffer containing 250mM calcium chloride and 20mM manganese chloride and 10mM HEPES buffer containing 20mM disodium hydrogen phosphate were mixed in a volume ratio of 1:1, mixing uniformly.
Step (3): 10mg of metallic palladium nanoparticles was added to the mixed solution obtained in the step (2), and stirred at room temperature for 4 hours. Centrifuging at 10000rpm for 5min, and washing with ultrapure water for 2-3 times to obtain Mn-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 160mg of polyvinylpyrrolidone and 0.1mL of formaldehyde solution were added thereto, respectively, and the reaction mixture was transferred to a reaction vessel and reacted at 100℃for 8 hours. Adding 5mL of acetone to precipitate nano particles, centrifuging at 12000rpm for 5min, and then washing with ethanol-acetone mixed solution and ultrapure water for 2-3 times to obtain metal palladium nano particles.
Step (2): 10mM Tris-HCl buffer containing 250mM calcium chloride and 20mM manganese chloride and 10mM HEPES buffer containing 6mM disodium hydrogen phosphate were mixed in a volume ratio of 1:1, mixing uniformly.
Step (3): 5mg of metallic palladium nanoparticles was added to the mixed solution obtained in the step (2), and stirred at room temperature for 4 hours. Centrifuging at 10000rpm for 5min, and washing with ultrapure water for 2-3 times to obtain Mn-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. The graph shows that the metal palladium nano particles modified by the manganese-doped calcium phosphide have smaller particle size, are uniformly distributed and have an average particle size of about 119.6 nm.
Example 12
With a power density of 1.0W/cm 2 The 808nm laser of the (2) is irradiated with manganese-doped calcium phosphide modified metal palladium nanoparticle suspension, and the temperature change in the irradiation period of 10 minutes is recorded. The result is shown in figure 3, and the temperature of the manganese-doped calcium phosphide-modified metal palladium nanoparticle suspension gradually rises along with the increase of the laser irradiation time, so that the nanoparticle has good photo-thermal conversion performance.
Example 13
The 3,3', 5' -tetramethyl benzidine method is adopted to detect the generation of hydroxyl free radicals after the manganese-doped calcium phosphide modified metallic palladium nanoparticle reacts for 5min under the conditions of pH7.4, pH6.5 and pH 6.0. As shown in figure 4, the manganese-doped calcium phosphide-modified metal palladium nanoparticle can generate more hydroxyl free radicals at the pH of 6.0, which indicates that the nanoparticle can generate Fenton reaction and has certain acid responsiveness.
Example 14
The capability of the manganese-doped calcium phosphide modified metal palladium nanoparticle to consume glutathione under the pH condition of 6.5 is detected by adopting a 5,5' -dithiobis (2-nitrobenzoic acid) method. As shown in fig. 5, the glutathione content gradually decreases with the time under the weak acidic condition, which indicates that the manganese-doped calcium phosphide-modified metallic palladium nanoparticle is expected to realize the glutathione depletion therapy when being used for the anti-tumor treatment.
Example 15
And detecting the biocompatibility of the manganese-doped calcium phosphide-modified metal palladium nanoparticle on human umbilical vein endothelial cells HUVEC by adopting an MTT method. HUVEC cells in logarithmic growth phase were inoculated into 96-well plates at 37deg.C and 5% CO by adjusting cell density to 7000 cells/well with DMEM medium containing 10% fetal bovine serum 2 Culturing overnight in an incubator. The blank group is a culture medium without medicines, the control group is a 4T1 cell liquid which is normally cultured without medicines, the experimental group is a culture medium containing manganese-doped calcium phosphide modified metal palladium nanoparticles with different concentrations, 6 holes are formed in each group, the culture is continued for 24 hours, the supernatant is discarded, the culture medium is washed for 3 times by using a sterile PBS buffer solution, 100 mu L of a serum-free culture medium containing MTT is added again, and the culture medium is incubated for 4 hours in a dark place. The supernatant was pipetted off, 150. Mu.L of DMSO solution was added to each well, shaken for 10 minutes, the absorbance at 490nm was measured with an microplate reader, and the cell viability was calculated. As shown in fig. 6, the result shows that the manganese-doped calcium phosphide modified metallic palladium nanoparticle has good safety.
Example 16
And detecting cytotoxicity of the manganese-doped calcium phosphide-modified metal palladium nanoparticle on breast cancer cells 4T1 by adopting an MTT method. Taking 4T1 cells in logarithmic phase, adjusting cell density to 7000 cells/well with 1640 medium containing 10% fetal bovine serum, inoculating into 96-well plate, inoculating into 5% CO at 37deg.C 2 Culturing overnight in an incubator. The blank group is a culture medium without medicines, the control group is 4T1 cell sap which is normally cultured without medicines, and the experimental group is metal palladium nanoparticle modified by manganese doped calcium phosphide with different concentrationsCulture medium, 6 compound holes per group, and experiment group after continuous culture for 12 hours gives 1.0W/cm 2 The laser was irradiated for 5 minutes. After 24h the supernatant was discarded and washed 3 times with sterile PBS buffer, 100. Mu.L of MTT-containing serum-free medium was added again and incubated for 4h in the absence of light. The supernatant was pipetted off, 150. Mu.L of DMSO solution was added to each well, shaken for 10 minutes, the absorbance at 490nm was measured with an microplate reader, and the cell viability was calculated. As shown in fig. 7, the result shows that the manganese doped calcium phosphide modified metal palladium nanoparticle after laser irradiation has a remarkable inhibition effect on 4T1 tumor cells.
Claims (4)
1. The manganese-doped calcium phosphide-modified metal palladium nanoparticle is characterized by being 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 formaldehyde solution, transferring the reaction solution into a hydrothermal reaction kettle for reaction, centrifuging and washing to obtain metal palladium nanoparticles;
(2) Mixing Tris-HCl solution containing a certain amount of calcium chloride and manganese chloride with HEPES solution containing disodium hydrogen phosphate to obtain a mixed solution;
(3) And (3) adding the metal palladium nanoparticle 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 nanoparticle.
2. The manganese-doped calcium phosphide-modified metal palladium nanoparticle as recited in claim 1, wherein the preparation method comprises the following steps:
(1) Dissolving 50-200 mg of palladium acetylacetonate in 10-30 mL 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 8000-12000 rpm for 5-10 min, and washing with ethanol-acetone mixed solution and ultrapure water for 2-3 times 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 the metal palladium nanoparticle obtained in the step (1) into 1-10 mL of the mixed solution obtained in the step (2), stirring, centrifuging and washing to obtain the manganese-doped calcium phosphide modified metal palladium nanoparticle.
3. A manganese-doped calcium phosphide-modified metallic palladium nanoparticle according to any one of claims 1 and 2, wherein the manganese-doped calcium phosphide-modified metallic palladium nanoparticle has an average particle diameter of 80 to 250nm.
4. A manganese-doped calcium phosphide-modified metallic palladium nanoparticle according to any one of claims 1 and 2, wherein the manganese-doped calcium phosphide-modified metallic palladium nanoparticle is useful in combination with photodynamic therapy for photothermal therapy of tumors.
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| CN102847952A (en) * | 2012-10-22 | 2013-01-02 | 安徽理工大学 | Method for preparing polyhedral nano palladium material through ethanol reduction |
| KR20200022275A (en) * | 2018-08-22 | 2020-03-03 | 고려대학교 산학협력단 | A Fabrication Method of Combustion Waves Based Palladium Oxides Composites And A Fabrication Method of pH Sensor |
| CN112546227A (en) * | 2021-01-15 | 2021-03-26 | 西南大学 | Preparation method of AIPH bismuth selenide loaded nanoparticles wrapped by calcium manganese phosphide |
| CN113368240A (en) * | 2021-06-13 | 2021-09-10 | 重庆医科大学 | Ferrocenyl metal-organic framework nanoparticle and preparation method thereof |
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| US20100055170A1 (en) * | 2008-08-26 | 2010-03-04 | Korea University Industrial & Academic Collaboration Foundation | Metal core nanocapsules |
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| CN102847952A (en) * | 2012-10-22 | 2013-01-02 | 安徽理工大学 | Method for preparing polyhedral nano palladium material through ethanol reduction |
| KR20200022275A (en) * | 2018-08-22 | 2020-03-03 | 고려대학교 산학협력단 | A Fabrication Method of Combustion Waves Based Palladium Oxides Composites And A Fabrication Method of pH Sensor |
| CN112546227A (en) * | 2021-01-15 | 2021-03-26 | 西南大学 | Preparation method of AIPH bismuth selenide loaded nanoparticles wrapped by calcium manganese phosphide |
| CN113368240A (en) * | 2021-06-13 | 2021-09-10 | 重庆医科大学 | Ferrocenyl metal-organic framework nanoparticle and preparation method thereof |
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