CN117304497A - Iridium dioxide composite metal organic framework material and application thereof - Google Patents
Iridium dioxide composite metal organic framework material and application thereof Download PDFInfo
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- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 title claims abstract description 38
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000011282 treatment Methods 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 206010006187 Breast cancer Diseases 0.000 claims abstract description 9
- 208000026310 Breast neoplasm Diseases 0.000 claims abstract description 9
- 239000002086 nanomaterial Substances 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 claims description 9
- 229920002385 Sodium hyaluronate Polymers 0.000 claims description 9
- 229940010747 sodium hyaluronate Drugs 0.000 claims description 9
- YWIVKILSMZOHHF-QJZPQSOGSA-N sodium;(2s,3s,4s,5r,6r)-6-[(2s,3r,4r,5s,6r)-3-acetamido-2-[(2s,3s,4r,5r,6r)-6-[(2r,3r,4r,5s,6r)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2- Chemical compound [Na+].CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 YWIVKILSMZOHHF-QJZPQSOGSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 239000005711 Benzoic acid Substances 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 235000010233 benzoic acid Nutrition 0.000 claims description 6
- VFHDWGAEEDVVPD-UHFFFAOYSA-N chembl507897 Chemical compound C1=CC(O)=CC=C1C(C1=CC=C(N1)C(C=1C=CC(O)=CC=1)=C1C=CC(=N1)C(C=1C=CC(O)=CC=1)=C1C=CC(N1)=C1C=2C=CC(O)=CC=2)=C2N=C1C=C2 VFHDWGAEEDVVPD-UHFFFAOYSA-N 0.000 claims description 6
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 claims description 6
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 230000001225 therapeutic effect Effects 0.000 abstract description 7
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 35
- 229920002674 hyaluronan Polymers 0.000 description 33
- 229960003160 hyaluronic acid Drugs 0.000 description 33
- 206010028980 Neoplasm Diseases 0.000 description 23
- 210000004027 cell Anatomy 0.000 description 19
- 230000000694 effects Effects 0.000 description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 238000007626 photothermal therapy Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
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- IZTQOLKUZKXIRV-YRVFCXMDSA-N sincalide Chemical compound C([C@@H](C(=O)N[C@@H](CCSC)C(=O)NCC(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CC(O)=O)C(=O)N[C@@H](CC=1C=CC=CC=1)C(N)=O)NC(=O)[C@@H](N)CC(O)=O)C1=CC=C(OS(O)(=O)=O)C=C1 IZTQOLKUZKXIRV-YRVFCXMDSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
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- VQVUBYASAICPFU-UHFFFAOYSA-N (6'-acetyloxy-2',7'-dichloro-3-oxospiro[2-benzofuran-1,9'-xanthene]-3'-yl) acetate Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(Cl)=C(OC(C)=O)C=C1OC1=C2C=C(Cl)C(OC(=O)C)=C1 VQVUBYASAICPFU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
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- 229910052737 gold Inorganic materials 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0057—Photodynamic therapy with a photosensitizer, i.e. agent able to produce reactive oxygen species upon exposure to light or radiation, e.g. UV or visible light; photocleavage of nucleic acids with an agent
- A61K41/0076—PDT with expanded (metallo)porphyrins, i.e. having more than 20 ring atoms, e.g. texaphyrins, sapphyrins, hexaphyrins, pentaphyrins, porphocyanines
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0063—Glycosaminoglycans or mucopolysaccharides, e.g. keratan sulfate; Derivatives thereof, e.g. fucoidan
- C08B37/0072—Hyaluronic acid, i.e. HA or hyaluronan; Derivatives thereof, e.g. crosslinked hyaluronic acid (hylan) or hyaluronates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention discloses an iridium dioxide composite metal organic framework material and application thereof, wherein the iridium dioxide composite metal organic framework material comprises IrO 2 -HA and PCN-224, said PCN-224 and IrO 2 The weight ratio of HA is 1:0.2 to 5 percent, the preparation method of the iridium dioxide composite metal organic framework material comprises the following steps: s1, preparation of PCN-224, S2 and preparation of IrO 2 -HA, S3, preparation of PCN-224-IrO 2 -HA; the nano material PCN-224-IrO provided by the invention 2 -HA, PCN-224 is prepared first, then in IrO 2 Surface-modified HA is loaded on the surface of PCN-224 to finally obtain PCN-224-IrO 2 HA. The nano material PCN-224-IrO 2 HA is used for the treatment of breast cancer with good therapeutic effects.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to an iridium dioxide composite metal organic framework material and application thereof.
Background
Metal Organic Frameworks (MOFs) have excellent controllability in structure and pore size and exhibit good superiority in terms of biodegradation and biocompatibility. The method is widely applied to the fields of drug targeted delivery, photodynamic therapy, catalysis and the like. When the MOFs are constructed by taking the photosensitizer as a ligand, the photosensitizer can be orderly arranged in the MOF structure, the phenomenon of quenching caused by aggregation of the photosensitizer is effectively avoided, and the porous structure in the MOFs can accelerate the diffusion of oxygen and Reactive Oxygen Species (ROS) and remarkably improve the treatment efficiency. Because of the strong tumor ablation effect of photothermal agents, the photothermal agents are of great interest in tumor treatment. Among the photothermal agents that have been used in the direction of tumor treatment are metal nanoparticles (Au, ag, cuS), fluorescent dyes, and carbon nanotubes.
Photodynamic therapy (PDT) has become an emerging modality for cancer treatment due to its minimal invasiveness, high selectivity and low toxicity to normal tissues/cells. Photodynamic therapy relies on light, photosensitizers, and oxygen to exert therapeutic effects at the cell site. However, in solid tumor cells, the action of photosensitizers is often hindered by a number of factors. Such as: the rapid growth of tumor tissue consumes a large amount of oxygen inside the tumor, so that the oxygen content in the tumor is severely reduced, and the conventional photosensitizer is aggregation-induced due to its hydrophobicity, so that the therapeutic drug cannot be effectively delivered to the vicinity of the tumor tissue, thereby reducing the therapeutic effect. Photothermal therapy (PTT) is an emerging tumor treatment method, and mainly utilizes a photothermal agent accumulated at a tumor part to strongly absorb near infrared light and convert light energy into heat energy in a short time when being irradiated by Near Infrared (NIR), so as to trigger temperature rise and realize the high-temperature ablation treatment effect on tumor tissues. The method for improving the absorption and conversion efficiency of the photothermal agent to near infrared light is one way for improving the PTT treatment effect. Most of the tumor treatments today are single in form, resulting in incomplete tumor ablation. The synergistic treatment of tumors using photodynamic therapy (PDT) and photothermal therapy (PTT) is an effective way to ameliorate the above problems.
Therefore, the iridium dioxide composite metal organic framework material and the application thereof are designed at present, and the photo-thermal/photodynamic synergistic treatment of tumors can be realized.
Disclosure of Invention
In order to solve the technical problems, the invention provides an iridium dioxide composite metal organic framework material.
The technical scheme of the invention is as follows: iridium dioxide composite metal organic framework material comprising IrO 2 -HA and PCN-224, said PCN-224 and IrO 2 The weight ratio of HA is 1:0.2 to 5 percent, the preparation method of the iridium dioxide composite metal organic framework material comprises the following steps:
s1, preparing PCN-224:
weighing 140-160 mg of zirconium oxychloride octahydrate and 45-60 mg of 5,10,15, 20-tetra (4-hydroxyphenyl) porphyrin (H) 2 TCPP), 1350-1450 mg of benzoic acid, zirconium oxychloride octahydrate, 5,10,15, 20-tetra (4-hydroxyphenyl) porphyrin (H) 2 TCPP) and benzoic acid are respectively dispersed in 10mL, 20mL and 20mL of N, N '-dimethylformamide, then all the materials are moved into a round-bottom flask to be stirred, reacted in an oil bath for 5 to 6 hours, centrifuged after being cooled to room temperature, washed three times by the N, N' -dimethylformamide and once by ethanol to obtain PCN-224;
s2, preparing IrO 2 -HA：
Weighing 4-6 mg of IrO 2 And 10-15 mg of sodium hyaluronate, dispersing the two together in a round bottom flask filled with 10mL of deionized water, adding 300-500 mu L of sodium hydroxide solution with the concentration of 1mol/L to adjust the pH, stirring at room temperature for 5-6 h, centrifuging after the reaction is finished, and collecting a sample to obtain IrO 2 -HA；
S3, preparation of PCN-224-IrO 2 -HA：
IrO is respectively carried out 2 Dispersing HA and PCN-224 together in a round bottom flask containing 2mL of absolute ethyl alcohol, stirring at normal temperature for 24-28 h, centrifuging after the reaction is finished, and collecting a sample to obtain PCN-224-IrO 2 -HA。
Description: the iridium dioxide composite metal organic framework material and the preparation method thereof provided by the invention firstly prepare PCN-224 and IrO 2 HA, irO is coordinated in proportion 2 The HA is loaded on the surface of the PCN-224 to prepare the PCN-224-IrO 2 HA. On the one hand, the method can improve the tumor hypoxia environment and provide more O for catalyzing and generating ROS by PCN-224 2 Improving PDT effect; on the other hand, under the irradiation of near infrared light (808 nm), the light energy can be converted into heat energy, and the tumor ablation effect is achieved by utilizing high temperature.
Further, in the step S1, the particle size of the prepared PCN-224 is 180-200 nm, and in the step S2, irO is added 2 The particle size of the particles is 48-52 nm.
Description: PCN-224 and IrO having the above particle size are used 2 So that the prepared PCN-224-IrO 2 HA HAs the advantage of enhanced catalytic activity, optimized physical properties.
Further, in the step S2, irO 2 The preparation method of (2) is as follows:
weighing 13-15 mg of iridium trichloride, dispersing the iridium trichloride in a round-bottom flask filled with 5mL of deionized water, regulating the pH to 13 by using a sodium hydroxide solution, stirring for 1-2 h at normal temperature, then reacting for 1-1.5 h in an oil bath, centrifugally collecting a sample after the reaction is finished, washing the sample with the deionized water for three times, and drying to obtain IrO 2 。
Description: irO prepared by the above method 2 The product has high purity and can be obtained with higher purity. This is important for subsequent applications and research, and the stirring of iridium trichloride in deionized water can achieve better uniform dispersion, the uniformly dispersed particles can provide larger surface area, increase the reaction rate and efficiency, and remove impurities and unreacted substances in the reaction by centrifugation and multiple times of washing, thereby improving IrO 2 Purity of (3). IrO prepared by the above method 2 The operation at normal temperature does not generate excessive energy loss or by-product generation.
Further, the temperature of the oil bath was 90 ℃.
Description: the temperature of the oil bath in the laboratory is often 90 ℃ and is used to control and maintain the stable temperature of the experiment.
Further, the concentration of the sodium hydroxide solution is 1mol/L.
Description: the use of 1mol/L sodium hydroxide can quickly and effectively raise the pH value of the solution, and the 1mol/L sodium hydroxide solution has higher concentration, so that the required pH value can be controlled more accurately in the use process.
Further, in the step S2, irO is first performed 2 The treatment was carried out under an air atmosphere and then mixed with sodium hyaluronate.
Description: treated IrO 2 Mixing with sodium hyaluronate to obtain IrO 2 HA capable of optimizing IrO 2 Performance and structure of HA.
Further, the air atmosphere cannot contain a gas that can react with oxygen.
Description: the air atmosphere cannot contain gas capable of reacting with oxygen, so that the optimized oxygen evolution catalytic performance of iridium dioxide can be ensured.
Further, the processing method comprises the following steps: irO is to be made into 2 Heating at a heating rate of 4-7 ℃/min, maintaining the temperature for 1h when the temperature is raised to 580 ℃, then heating to 720 ℃ at a heating rate of 6-9 ℃/min and maintaining the temperature for 3h, then heating to 740 ℃ at a heating rate of 4-7 ℃/min and maintaining the temperature for 1h, and finally slowly cooling to room temperature.
Description: irO can be changed by the above-mentioned process 2 The properties of crystal structure, grain size, crystallinity and the like, improve IrO 2 Improving the chemical stability of the crystal lattice of (a) and, in addition, modifying IrO 2 The grain size and distribution of the particles can further regulate the bioactivity and the drug release performance.
Further, the room temperature in the steps S1 and S2 means 21-25 ℃.
Further, the nanomaterial PCN-224-IrO 2 HA is used for the treatment of breast cancer.
Description: irO on the one hand 2 Catalytic H 2 O 2 Oxygen is generated, the tumor hypoxia environment is improved, and more O is provided for catalyzing the generation of ROS by PCN-224 2 Improving PDT effect; irO on the other hand 2 Under the irradiation of near infrared light (808 nm), the light energy is converted into heat energy, and the tumor ablation effect is achieved by utilizing high temperature, PCN-224-IrO 2 -HA for use in therapyThe breast cancer has outstanding effect.
The beneficial effects of the invention are as follows:
(1) The nano material PCN-224-IrO provided by the invention 2 HA, PCN-224 and IrO were synthesized separately by first oil bath at 90 DEG C 2 Then in IrO 2 Surface-modified HA is loaded on the surface of PCN-224 to finally obtain PCN-224-IrO 2 HA. PCN-224-IrO of the nano material 2 HA is used for treating breast cancer, HAs good therapeutic effect, and is IrO 2 Catalytic H 2 O 2 Generates oxygen and provides more O for catalyzing PCN-224 to generate ROS 2 The method comprises the steps of carrying out a first treatment on the surface of the IrO on the other hand 2 Under the irradiation of near infrared light (808 nm), the light energy is converted into heat energy, and the tumor ablation effect is achieved by utilizing high temperature.
(2) There are MOF-loaded photothermal agents that achieve photothermal/photodynamic synergistic therapeutic effects on tumors, such as CuS. Compared with the material, the material is iridium dioxide with targeting group Hyaluronic Acid (HA) compositely modified through coordination, and importantly, the iridium dioxide HAs a photothermal treatment effect and can catalyze H 2 O 2 Oxygen is generated, the oxygen deficiency in the tumor is relieved, and the tumor treatment effect can be effectively improved.
Drawings
FIG. 1 is a TEM image of PCN-224;
FIG. 2 is a TEM image of IrO 2;
FIG. 3 is a TEM image of PCN-224-IrO 2-HA;
FIG. 4 is an ultraviolet absorbance spectra of H2TCPP, PCN-224;
FIG. 5 is an ultraviolet absorbance spectrum of IrO 2;
FIG. 6 is a graph of fluorescence emission spectra of PCN-224 at various illumination times;
FIG. 7 is a graph of fluorescence emission spectra of PCN-224-IrO2-HA at various illumination times;
FIG. 8 is a graph of fluorescence emission spectra under different conditions;
FIG. 9 is PCN-224 and IrO 2 -uv absorption spectra of HA in different proportions;
FIG. 10 is PCN-224 and IrO 2 Fluorescence absorption of HA in different proportionsA spectrogram;
FIG. 11 is PCN-224 and IrO 2 -photothermograms of different proportions of HA;
FIG. 12 is a graph of LO2 cell activity assay;
FIG. 13 is a graph showing the detection of 4T1 cell activity.
Detailed Description
The invention will be described in further detail with reference to the following embodiments to better embody the advantages of the invention.
Example 1
Iridium dioxide composite metal organic framework material is characterized by comprising IrO 2 -HA and PCN-224, said PCN-224 and IrO 2 The weight ratio of HA is 1: the preparation method of the iridium dioxide composite metal organic framework material comprises the following steps:
s1, preparing PCN-224:
160mg of zirconium oxychloride octahydrate and 60mg of 5,10,15, 20-tetra (4-hydroxyphenyl) porphyrin (H) were weighed out 2 TCPP), 1450mg of benzoic acid, zirconium oxychloride octahydrate, 5,10,15, 20-tetrakis (4-hydroxyphenyl) porphyrin (H) 2 TCPP) and benzoic acid are respectively dispersed in 10mL, 20mL and 20mL of N, N '-dimethylformamide, then all the materials are moved into a round-bottom flask to be stirred, reacted for 6 hours in an oil bath, centrifuged after being cooled to 24 ℃, washed three times by the N, N' -dimethylformamide and once by ethanol to obtain PCN-224; the particle size of the prepared PCN-224 is 200nm.
S2, preparing IrO 2 -HA：
Weigh 5mg of IrO 2 And 10mg of sodium hyaluronate, dispersing the two together in a round bottom flask containing 10mL of deionized water, adding 500. Mu.L of sodium hydroxide solution to adjust pH, stirring at 24 ℃ for 6 hours, centrifuging after the reaction is finished, and collecting a sample to obtain IrO 2 -HA; the concentration of the sodium hydroxide solution is 1mol/L;
IrO 2 the preparation method of (2) is as follows:
15mg of iridium trichloride was weighed, dispersed in a round-bottomed flask containing 5mL of deionized water, pH was adjusted to 13 with 1mol/L sodium hydroxide solution, and stirred at room temperature for 1h, followed byCarrying out reaction in an oil bath for 1h, centrifugally collecting a sample after the reaction is finished, washing with deionized water for three times, and drying to obtain IrO 2 The method comprises the steps of carrying out a first treatment on the surface of the IrO prepared 2 The grain diameter is 50nm;
s3, preparation of PCN-224-IrO 2 -HA：
IrO is respectively carried out 2 dispersing-HA and PCN-224 together in a round-bottomed flask containing 2mL of absolute ethanol, stirring at 24 ℃ for 24 hours, centrifuging after the reaction is finished, and collecting a sample to obtain PCN-224-IrO 2 -HA; PCN-224-IrO of the nano material 2 -HA is used for the treatment of breast cancer;
the temperature of the oil bath was 90 ℃.
Example 2
This example differs from example 1 in that the iridium dioxide composite metal-organic framework material is characterized by comprising IrO 2 -HA and PCN-224, said PCN-224 and IrO 2 The weight ratio of HA is 3:1.
Example 3
This example differs from example 1 in that the iridium dioxide composite metal-organic framework material is characterized by comprising IrO 2 -HA and PCN-224, said PCN-224 and IrO 2 The weight ratio of HA is 1:1.
Example 4
This example differs from example 1 in that the iridium dioxide composite metal-organic framework material is characterized by comprising IrO 2 -HA and PCN-224, said PCN-224 and IrO 2 The weight ratio of HA is 1:5.
Example 5
This example differs from example 1 in that the iridium dioxide composite metal-organic framework material is characterized by comprising IrO 2 -HA and PCN-224, said PCN-224 and IrO 2 The weight ratio of HA is 5:1.
Example 6
This embodiment is different from embodiment 1 in that in step S2, irO is first performed 2 Treating under air atmosphere, and mixing with sodium hyaluronate;
the processing method comprises the following steps:IrO is to be made into 2 Heating at a heating rate of 6 ℃/min, maintaining the temperature for 1h when the temperature is raised to 580 ℃, then heating to 720 ℃ at a heating rate of 8 ℃/min and maintaining the temperature for 3h, then heating to 740 ℃ at a heating rate of 5.5 ℃/min and maintaining the temperature for 1h, and finally slowly cooling to 24 ℃, wherein the air atmosphere cannot contain gas capable of reacting with oxygen.
Example 7
In the step S2, irO is first added 2 Treating under air atmosphere, and mixing with sodium hyaluronate;
the processing method comprises the following steps: irO is to be made into 2 Heating at a heating rate of 4 ℃/min, maintaining the temperature for 1h when the temperature is raised to 580 ℃, then heating to 720 ℃ at a heating rate of 6 ℃/min and maintaining the temperature for 3h, then heating to 740 ℃ at a heating rate of 4 ℃/min and maintaining the temperature for 1h, and finally slowly cooling to 24 ℃, wherein the air atmosphere cannot contain gas capable of reacting with oxygen.
Example 8
In the step S2, irO is first added 2 Treating under air atmosphere, and mixing with sodium hyaluronate;
the processing method comprises the following steps: irO is to be made into 2 Heating at a heating rate of 7 ℃/min, maintaining the temperature for 1h when the temperature is raised to 580 ℃, then heating to 720 ℃ at a heating rate of 9 ℃/min and maintaining the temperature for 3h, then heating to 740 ℃ at a heating rate of 7 ℃/min and maintaining the temperature for 1h, and finally slowly cooling to 24 ℃, wherein the air atmosphere cannot contain gas capable of reacting with oxygen.
Experimental example
The iridium dioxide composite metal-organic frame materials prepared by the methods of the above examples 1 to 8 were used to detect and record data;
1. PCN-224 and IrO prepared in example 1 were subjected to a Transmission Electron Microscope (TEM) 2 PCN-224-IrO 2 -morphology and size of HA is detected;
as shown in FIGS. 1, 2 and 3, PCN-224 is about 200nm and IrO 2 About 50nm in size, PCN-224-IrO2-HA about 220nm, PCN-224 and IrO 2 The morphology is uniformSpherical shape.
2. For PCN-224 and IrO prepared in example 1 2 H 2 TCPP carries out ultraviolet absorption detection;
at the same time to H 2 The TCPP performs ultraviolet absorption detection and comparison;
as shown in FIGS. 4 and 5, with an organic ligand H 2 Compared with TCPP, the ultraviolet absorption peak of PCN-224 is red shifted due to the increase of the conjugation area of porphyrin and IrO 2 There is also a broader absorption band.
3. For PCN-224, PCN-224-IrO prepared in example 1 2 -HA performs active oxygen detection;
since 2',7' -dichlorofluorescein diacetate (DCFH-DA) can be oxidized by ROS to form DCF with green fluorescence, as shown in FIGS. 6, 7 and 8, PCN-224-IrO 2 The HA+laser group HAs the strongest fluorescence intensity due to IrO 2 Capable of catalyzing the production of more O 2 More ROS are produced by PCN-224 photocatalysis.
4. Investigation of PCN-224 and IrO 2 Different proportions of-HA to PCN-224-IrO 2 The influence of HA was compared with examples 1 to 5 as experimental examples, and UV detection and fluorescence detection were performed, respectively;
as shown in fig. 9, 10, and 11, found in IrO 2 A special case arises during the gradual increase of the specific gravity of HA, namely in PCN-224:IrO 2 At-ha=1:3, both the ultraviolet absorption peak and the fluorescence absorption peak of the material show inflection points, and start to show a downward trend. By combining PCN-224 with IrO in different proportions 2 Photothermal data for HA found in PCN-224:IrO 2 -PCN-224-IrO when ha=1:3 2 The photothermal effect of HA is best, with a decrease in photothermal results at a ratio of 1:5. The optimal recombination ratio is PCN-224:iro 2-ha=1:3.
5. The effects of different treatment methods and concentrations on cells were investigated, and cytotoxicity detection was performed using example 1 as a test example for comparison;
cytotoxicity on mouse breast cancer cells (4T 1) and human normal hepatocytes (LO 2) was studied by CCK-8, 4T1, LO2 cells were seeded into 96-well plates at a cell density of 8×10 4 After culturing in a constant temperature incubator at 37℃for 12 hours, the cells were observed and after the cells were attached to each other, the old cell culture medium was discarded. PCN-224-IrO with different concentrations was added to a 96-well plate 2 Fresh culture medium of-HA was continued for PCN-224-IrO 2 The concentration gradients of HA were 0, 10, 20, 30, 40, 50 and 60. Mu.g/mL.
Adding PCN-224-IrO with different concentrations 2 After 4 hours of incubation with fresh medium of HA, the incubation was continued for 18 hours with 650nm, 808nm lasers for 10 minutes and 650 nm+806 nm double lasers for 10 minutes, respectively. After the incubation, the old cell culture medium is discarded, the diluted CCK-8 fresh culture medium is added, and the survival rate of the cells in different groups is detected by using an enzyme-labeled instrument.
The results are shown in FIGS. 12 and 13, PCN-224-IrO 2 When the HA concentration was 60. Mu.g/mL and no light was applied, the 4T1 cell (Normal group of FIG. 13) survival rate was about 85%, and the LO2 cell survival rate was 85% or more. The viability of 4T1 cells was reduced after irradiation with a single 650nm laser (FIG. 13PDT group), due to the ability of the PCN-224 material to drive intracellular O under laser irradiation 2 Converts to ROS. After irradiation with a single 808nm laser (PTT group of FIG. 13), the IrO is used 2 The material can convert light energy into heat energy, 4T1 cells are ablated at high temperature, and the survival rate is also reduced. On the other hand, after being irradiated by 650nm+808nm double lasers (shown in a 13PDT+PTT group), the survival rate of 4T1 cells is obviously and greatly reduced, which is attributed to two aspects, on the one hand, after being catalyzed by IrO2 materials, the content of O2 in the cells is improved, and the PDT effect is enhanced; on the other hand, irO2 materials generate high temperatures under laser irradiation, which can achieve PTT effects on cells. The results show that PDT+PTT synergistic treatment effect is better.
6. Exploration of IrO 2 The effects on PCN-224-IrO2-HA were compared with examples 1, 6 to 8 as experimental examples;
study of PCN-224-IrO by CCK-8 2 Cytotoxicity of mouse breast cancer cells (4T 1) after having HA concentration of 60. Mu.g/mL and having undergone 650 nm+806 nm double laser irradiation was tested as follows;
TABLE 1 Activity of mouse breast cancer cells
As is clear from Table 1, the PCN-224-IrO obtained by the preparation method of example 7 can be obtained by comparing example 1 with examples 6 to 8 2 The therapeutic effect of HA was improved over example 1, for IrO 2 Preparation of PCN-224-IrO after treatment in an air atmosphere 2 -HA, p-PCN-224-IrO 2 The therapeutic effect of HA is improved to some extent.
Claims (9)
1. Iridium dioxide composite metal organic framework material is characterized by comprising IrO 2 -HA and PCN-224, said PCN-224 and IrO 2 The weight ratio of HA is 1:0.2 to 5 percent, the preparation method of the iridium dioxide composite metal organic framework material comprises the following steps:
s1, preparing PCN-224:
weighing 140-160 mg of zirconium oxychloride octahydrate and 45-60 mg of 5,10,15, 20-tetra (4-hydroxyphenyl) porphyrin (H) 2 TCPP), 1350-1450 mg of benzoic acid, zirconium oxychloride octahydrate, 5,10,15, 20-tetra (4-hydroxyphenyl) porphyrin (H) 2 TCPP) and benzoic acid are respectively dispersed in 10mL, 20mL and 20mL of N, N '-dimethylformamide, then all the materials are moved into a round-bottom flask to be stirred, reacted in an oil bath for 5 to 6 hours, centrifuged after being cooled to room temperature, washed three times by the N, N' -dimethylformamide and once by ethanol to obtain PCN-224;
s2, preparing IrO 2 -HA：
Weighing 4-6 mg of IrO 2 And 10-15 mg of sodium hyaluronate, dispersing the two together in a round bottom flask filled with 10mL of deionized water, adding 300-500 mu L of sodium hydroxide solution with the concentration of 1mol/L to adjust the pH, stirring at room temperature for 5-6 h, centrifuging after the reaction is finished, and collecting a sample to obtain IrO 2 -HA；
S3, preparation of PCN-224-IrO 2 -HA：
IrO is respectively carried out 2 HA and PCN-224 were dispersed together in a round bottom flask containing 2mL of absolute ethanol followed by stirring at room temperature 24After the reaction is finished, centrifugally collecting a sample to obtain PCN-224-IrO 2 -HA。
2. The iridium dioxide composite metal-organic framework material according to claim 1, wherein in the step S1, the particle size of the prepared PCN-224 is 180-200 nm, and in the step S2, irO is prepared 2 The particle size of the particles is 48-52 nm.
3. The iridium dioxide composite metal-organic framework material according to claim 1, wherein in the step S2, irO 2 The preparation method of (2) is as follows:
13-15 mg of iridium trichloride is weighed, dispersed in a round-bottom flask filled with 5mL of deionized water, pH=13 is regulated by sodium hydroxide solution, and stirred for 1-2 h at normal temperature, then reacted for 1-1.5 h in an oil bath, after the reaction is finished, the sample is centrifugally collected, washed three times by the deionized water and dried to obtain IrO 2 。
4. An iridium dioxide composite metal-organic framework material as claimed in claim 3 wherein the temperature of the oil bath is 90 ℃.
5. An iridium dioxide composite metal-organic framework material as claimed in claim 3, wherein the concentration of sodium hydroxide solution is 1mol/L.
6. The iridium dioxide composite metal-organic framework material according to claim 1, wherein in the step S2, irO is first added 2 The treatment was carried out under an air atmosphere and then mixed with sodium hyaluronate.
7. The iridium dioxide composite metal-organic framework material as claimed in claim 6, wherein the treatment method comprises the following steps: irO is to be made into 2 Heating at a heating rate of 4-7deg.C/min, maintaining the temperature at 580 deg.C for 1h, heating to 720 deg.C at a heating rate of 6-9deg.C/min and maintaining the temperature for 3h, and heating to 740 deg.C at a heating rate of 4-7deg.C/min and maintaining the temperatureAnd (3) 1h, and finally, slowly cooling to room temperature.
8. The iridium dioxide composite metal-organic framework material according to claim 1, wherein in the step S1, the particle size of the prepared PCN-224 is 180-200 nm, and in the step S2, irO is prepared 2 The particle size of the particles is 48-52 nm.
9. Use of iridium dioxide composite metal-organic framework material as claimed in any one of claims 1 to 8, wherein the nanomaterial PCN-224-IrO 2 HA is used for the treatment of breast cancer.
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