CN109535436B - Metalloporphyrin framework material with hollow nano structure and preparation method and application thereof - Google Patents
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Abstract
The invention belongs to the field of nano materials, and relates to a metalloporphyrin framework material with a hollow nano structure, and a preparation method and application thereof. The material has a huge cavity and a shell, and the shell is made of metalloporphyrin framework material. The size of the nano material is 20-200nm, the thickness of a shell layer is 5-50nm, and the diameter of a cavity is 10-200 nm. The huge cavity of the hollow PMOF nano particle is used for loading perfluorocarbon, the perfluorocarbon has high oxygen dissolving performance, and can efficiently load oxygen to provide more oxygen for photodynamic therapy, so that more singlet oxygen is generated, and the photodynamic curative effect is enhanced. The huge cavity and shell pores of the hollow PMOF nano particles can efficiently load diagnosis and treatment reagents, including chemotherapeutic drugs, photo-thermal reagents, imaging molecules and the like. The hollow PMOF has wide application prospect as a nano drug-carrying system.
Description
Technical Field
The invention belongs to the field of nano materials, and particularly relates to a metalloporphyrin framework material with a hollow nano structure, and a preparation method and application thereof.
Background
Metal-organic frameworks (MOFs) are a novel class of organic-inorganic hybrid porous materials, and are formed by connecting Metal ions or Metal cluster nodes and organic ligands. The MOFs material has excellent characteristics of extremely large specific surface area, porosity, adjustable pore size, controllable chemical structure and composition of shape, good biodegradability and the like, so that the MOFs material is used as a novel nano-carrier platform and has great application potential in the field of biomedicine.
Metalloporphyrin framework (PMOF) is a three-dimensional stable ordered space network structure formed by coordination of metal ions or metal ion clusters and carboxylic porphyrin ligands with photosensitive activity. The photosensitizer porphyrin molecule is used as an organic ligand to directly participate in the construction of PMOF, so that the high-efficiency loading of the photosensitizer is realized, and the decrease of the yield of active oxygen quantum caused by the aggregation of the photosensitizer molecule is avoided, therefore, the PMOF has excellent photocatalytic activity and photodynamic effect.
Photodynamic therapy is a new treatment means in recent years, and has the advantages of good controllability, small side effect and the like. The principle is that the photosensitizer activates surrounding oxygen molecules to generate active oxygen under the excitation of a light source, so that the important structure and function of cells are damaged, and finally the purpose of destroying pathological tissues is achieved. Oxygen is an important condition indispensable for the generation of active oxygen by light activation. However, the hypoxic character of most diseased tissues significantly reduces the photodynamic therapy effect, and photodynamic therapy is a rapid oxygen-consuming process, which causes a domino effect and further inhibits photodynamic therapy. Therefore, ensuring sufficient oxygen supply during photodynamic therapy becomes a major challenge to be solved in photodynamic therapy.
The use of the nano drug-carrying system promotes the delivery of drugs, particularly hydrophobic drugs, in vivo, improves the stability and targeting property of the drugs, improves the bioavailability of the drugs, remarkably reduces the toxic and side effects of the drugs, can realize the sustained release of the drugs, and becomes a hotspot in the current medical research field. Achieving efficient loading of drugs remains a constantly sought goal of nano drug delivery systems.
Disclosure of Invention
In order to solve the problems, the invention provides a metalloporphyrin framework material with a hollow nano structure. The metalloporphyrin framework material with the hollow nano structure has huge cavities and highly ordered shell pores, and on one hand, the metalloporphyrin framework material can be used for loading perfluorocarbons, providing sufficient oxygen for photodynamic therapy and enhancing photodynamic effect; on the other hand, various diagnosis and treatment reagents can be efficiently loaded.
In a first aspect, the present invention provides a hollow nanostructureThe metalloporphyrin framework material consists of a cavity and a shell, wherein the shell is made of Zr6Cluster (Zr)6O4(OH)4(H2O)6(OH)6(COO)6) And tetracarboxylic acid ligand 5,10,15, 20-tetrakis (4-carboxyphenyl) porphyrin (5, 10,15, 20-tetrapkis (4-carboxyphenyl) porphyrin (H) having photosensitizing activity2TCPP)) through coordination, a three-dimensional stable ordered spatial network structure.
Preferably, the size of the metalloporphyrin framework material with the hollow nano structure is 20-200nm, and the thickness of the shell layer is 5-50 nm.
In a second aspect, the present invention provides a method for preparing a metalloporphyrin framework material (hollow PMOF) with a hollow nanostructure, comprising the steps of:
(a) preparing inorganic nano particles as sacrificial templates;
(b) dispersing the inorganic nano particles prepared in the step (a) in a solvent, and adding a zirconium (Zr) source and an organic ligand H2TCPP and auxiliary regulating ligand, wherein the auxiliary regulating ligand is benzoic acid, acetic acid, formic acid, trifluoroacetic acid or hydrochloric acid, the mixture is heated and reacted at 70-150 ℃, and then products are collected by centrifugation, and the nanometer composite material with inorganic nanometer particles as cores and metal porphyrin framework materials as shells is obtained by washing;
(c) and (c) etching the nano composite material obtained in the step (b), and removing the inorganic nano particle core to obtain the metalloporphyrin framework material with the hollow nano structure.
The inorganic nanoparticles in the step (a) comprise cuprous oxide, silicon dioxide, ferroferric oxide, titanium dioxide, manganese oxide, aluminum oxide, zinc oxide, calcium phosphate and the like.
Preferably, the size of the inorganic nanoparticles of step (a) is 10-200nm, and the size of the inorganic nanoparticles determines the size of the hollow PMOF cavity. The diameter of the cavity is 10-200 nm.
The solvent for dispersing the inorganic nano particles in the step (b) is one or more of N, N-dimethylformamide, water, methanol and ethanol.
The reaction temperature in step (b) is preferably 80 to 120 ℃.
Zirconium (Zr) source, organic ligand H2TCPP and the auxiliary regulating ligand are precursors of metalloporphyrin framework materials.
The Zr source is a soluble compound containing Zr, preferably the Zr source is ZrCl4、ZrOCl2·8H2And O. Preferably, the co-regulatory ligand is benzoic acid.
Zr source, organic ligand H in PMOF precursor2The molar ratio of TCPP to the co-regulating ligand is (5-10): 1: (100-). sub.300.
Changing Zr source and organic ligand H in added PMOF precursor2The amounts of TCPP and co-regulator ligand allow PMOF with different shell thicknesses to be obtained.
In the step (c), the inorganic nanoparticle cores are removed from the nano composite material obtained in the step (b), the nano composite material taking cuprous oxide, ferroferric oxide, titanium dioxide, manganese oxide, aluminum oxide, zinc oxide and calcium phosphate as the cores is etched by acid, the nano composite material taking silicon dioxide as the cores is etched by alkali or hydrofluoric acid, and besides, different etching methods can be adopted according to different inorganic nanoparticle cores.
The acid for acid etching is hydrochloric acid, sulfuric acid, hydrofluoric acid or nitric acid.
The alkali used for alkali etching is sodium hydroxide, potassium hydroxide or sodium carbonate.
Preferably, the acid for acid etching has a pH of 0 to 3. The pH of the alkali used for alkali etching is 7-11.
In a third aspect, the invention provides an application of a metalloporphyrin framework material with a hollow nanostructure, which comprises the following two aspects:
(a) the giant cavity in the metalloporphyrin framework material with the hollow nano structure is used for loading perfluorocarbon, and the high oxygen dissolving performance of the perfluorocarbon is utilized to provide sufficient oxygen for the hollow PMOF, so that more singlet oxygen is generated, and the photodynamic effect is enhanced.
(b) The huge cavity and shell pores in the metalloporphyrin framework material with the hollow nano structure can efficiently load diagnosis and treatment reagents, including chemotherapeutic drugs, photo-thermal reagents, imaging molecules and the like.
In summary, the beneficial effects of the invention include the following aspects.
1. The metalloporphyrin framework material with the hollow nano structure, namely the hollow PMOF, realizes the high-efficiency loading of the photosensitizer due to the fact that the photosensitizer porphyrin molecules directly participate in the construction of the hollow PMOF as organic ligands, and simultaneously avoids the reduction of the yield of active oxygen quantum caused by the aggregation of the photosensitizer molecules, so that the hollow PMOF has excellent photocatalytic activity and photodynamic effect.
2. The metalloporphyrin framework material with the hollow nano structure has a huge cavity, is used for loading perfluorocarbon, and provides sufficient oxygen for hollow PMOF by utilizing the high oxygen dissolving performance of the perfluorocarbon, so that more singlet oxygen is generated, and the photodynamic treatment effect is enhanced.
3. The metalloporphyrin framework material with the hollow nano structure has huge cavities and shell pores, and can efficiently load diagnosis and treatment reagents.
Drawings
FIG. 1 shows Cu prepared in example 12Transmission electron microscopy of O @ PMOF nanocomposite;
FIG. 2 is a transmission electron micrograph of a hollow PMOF prepared in example 1;
FIG. 3 is an X-ray powder diffraction pattern of the hollow PMOF prepared in example 1;
FIG. 4 is a graph of the particle size distribution of the hollow PMOF prepared in example 1;
FIG. 5 shows the singlet oxygen generation of medium mass concentration hollow PMOF and perfluoro compound-loaded hollow PMOF from example 3.
Detailed Description
While the preferred embodiments of the present invention are described below, it should be understood that various changes and modifications can be made by one skilled in the art without departing from the principles of the invention, and such changes and modifications are also considered to be within the scope of the invention.
Example 1:
the preparation of metalloporphyrin framework material with hollow nano structure includes the following steps:
(1) adding 0.001molCuAc2·3H2O and 0.01mol polyvinylpyrrolidone (PVP, MW 30000) were dissolved in 30.0mL of ethylene glycol. Then, 10.0mL of NaOH (2.0 mol. L) was added dropwise to the above solution-1) Stirring was continued for 0.5h, and 10.0mL of ascorbic acid solution (0.3 mol. L) was added-1) Then, the reaction was carried out at 55 ℃ for 30 minutes. After the product was collected by centrifugation, it was washed with water 3 times to obtain Cu2And (4) O nanoparticles.
(2) Mixing 10mg of Cu2Dispersing O nano particles in 10mL of DMF, adding 0.093mmol of ZrOCl2·8H2O、0.013mmol H2TCPP and 2.30mmol benzoic acid, heating at 90 ℃ for reaction for 5h, cooling to room temperature after the reaction is finished, centrifuging to collect the product, and washing with DMF for 3 times to obtain Cu2Nanocomposite Cu with O as core and PMOF as shell2O@PMOF。
(3) Mixing Cu2O @ PMOF dispersed in 50mL HCl (0.1 mol. L)-1) And stirring for 24 hours at room temperature, centrifuging to collect a product, and washing with primary water for 5 times to obtain the hollow PMOF.
FIG. 1 shows Cu prepared in example 12Transmission electron micrograph of O @ PMOF nanocomposite, from which it can be seen that Cu prepared in this example2The grain diameter of the O @ PMOF nano composite material is 110-150nm, and the shell thickness is 20-25 nm.
FIG. 2 is a transmission electron micrograph of the hollow PMOF prepared in example 1, which shows that the hollow PMOF prepared in this example is a hollow nanosphere with a particle size of 110-150nm and a shell thickness of 20-25 nm.
FIG. 3 is an X-ray powder diffraction pattern of the hollow PMOF prepared in example 1, from which it can be seen that the hollow PMOF prepared in this example is 4.5o、6.4o、7.9o、9.1o、11.2oThe prepared hollow PMOF has a characteristic diffraction peak, a sharp diffraction peak type and high diffraction intensity, and shows that the prepared hollow PMOF has good crystallinity.
FIG. 4 is a graph showing the particle size distribution of the hollow PMOF obtained in example 1, as measured by dynamic light scattering, and it can be seen that the hollow-PMOF obtained in this example has a relatively uniform particle size distribution, an average hydrated particle size of 255.1nm, a PDI of 0.089, and good monodispersity.
Example 2:
the preparation of metalloporphyrin framework material with hollow nano structure includes the following steps:
(1) 74mL of ethanol and 10mL of H2O and 3.14mL of ammonia solution were mixed and stirred at 30 ℃ for 0.5 h. Then, 6mL of ethyl silicate was quickly added to the above solution, and the reaction was continued for 1 hour. After the product was collected by centrifugation, it was washed 3 times with ethanol and water, respectively, to obtain SiO2And (3) nanoparticles.
(2) Mixing 10mg of SiO2Dispersed in 10mL of primary water, 10mL of PVP (20 mg. mL) was added-1) Stirring at room temperature for 12h, centrifuging to collect the product, washing with primary water for 3 times to obtain SiO with surface modified PVP2Nano SiO particle2@PVP。
(3) Mixing 10mg of SiO2@ 0.093mmol of ZrOCl is added into the nano-particles dispersed in 10mL of DMF2·8H2O、0.013mmol H2TCPP and 2.3mmol benzoic acid, heating at 110 deg.C for 5h, cooling to room temperature after reaction, centrifuging to collect product, washing with DMF for 3 times to obtain SiO2Nanocomposite SiO with core and PMOF shell2@PMOF。
(4) Mixing SiO2@ PMOF dispersed in 50mL Na2CO3（0.4mol·L-1) And (3) reacting in the solution at 50 ℃ for 10h, cooling to room temperature after the reaction is finished, centrifuging to collect a product, and washing with primary water for 5 times to obtain the hollow PMOF.
Example 3: photodynamic effect of perfluorohexane-loaded metalloporphyrin framework material with hollow nanostructure
Perfluorohexane (PFH) was supported on the metalloporphyrin framework material (hollow PMOF) having a hollow nanostructure prepared in example 1 of the present invention, and a Perfluorohexane (PFH) -supported hollow PMOF was obtained, and the photodynamic effect was verified. With hollow PMOF as a control, the procedure was as follows:
(1) to 3mL hollow PMOF (10 ug mL)-1) 15uLDPBF solution (10 mol. L) was added to the dispersion-1) 660nm laser (500 mW cm)-2) The change in the absorption value of 1, 3-Diphenylisobenzofuran (DPBF) at a wavelength of 467nm was measured using UV-Vis for different periods of irradiation, and the occurrence of singlet oxygen in the hollow PMOF was measured, and the results are shown in FIG. 5.
(2) To 3mL PFH @ hollow PMOF (10 ug mL)-1) 15uL of DPBF solution (10 mol. L) was added to the dispersion-1) 660nm laser (500 mW cm)-2) The change in absorbance of DPBF at 467nm wavelength was measured by UV-Vis under different irradiation times, and the occurrence of singlet oxygen in PFH @ hollow PMOF was measured, and the results are shown in FIG. 5.
As can be seen from FIG. 5, at the same concentration, the absorbance of DPBF of PFH @ hollow PMOF is decreased more rapidly than that of hollow PMOF, and the overall decrease is more than that of hollow PMOF, because PFH has high oxygen-dissolving property and can provide sufficient oxygen for hollow PMOF, thereby generating more singlet oxygen and enhancing the photodynamic effect.
Example 4 hollow PMOF for high-potency Loading of chemotherapeutic Agents Adriamycin
The result of the fact that doxorubicin (Dox) is loaded in the metalloporphyrin framework material (hollow PMOF) with the hollow nanostructure prepared in the embodiment 1 of the invention, and the load of the hollow PMOF to the doxorubicin is measured to be 2.2mg Dox/mg MOF, which is much higher than the load of the currently reported metal organic framework nanomaterial to Dox, because the hollow PMOF has huge cavities and highly ordered shell pores, a large amount of drugs can be loaded, and the result shows that the hollow PMOF is a nano drug loading system with great application potential.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (7)
1. The preparation method of the metalloporphyrin framework material with the hollow nano structure comprises the steps of preparing a hollow nano structure, preparing a shell, and preparing a metal porphyrin framework material with the hollow nano structure from a hollow cavity and the shell, wherein the shell is made of Zr6Cluster and tetracarboxylic acid ligand 5,10,15, 20-tetra (4-carboxyphenyl) porphyrin with photosensitive activity form a three-dimensional stable ordered space network structure through coordination;
the method is characterized by comprising the following steps:
(a) preparing inorganic nanoparticles, wherein the inorganic nanoparticles comprise cuprous oxide, silicon dioxide, ferroferric oxide, manganese oxide, titanium dioxide, aluminum oxide, zinc oxide or calcium phosphate;
(b) dispersing the inorganic nano particles prepared in the step (a) in a solvent, and adding a zirconium source and an organic ligand H2TCPP and auxiliary regulating ligand, wherein the auxiliary regulating ligand is benzoic acid, acetic acid, formic acid, trifluoroacetic acid or hydrochloric acid, the mixture is heated and reacted at 70-150 ℃, and then products are collected by centrifugation, and the nanometer composite material with inorganic nanometer particles as cores and metal porphyrin framework materials as shells is obtained by washing;
(c) and (c) etching the nano composite material obtained in the step (b), and removing the inorganic nano particle core to obtain the metalloporphyrin framework material with the hollow nano structure.
2. The method according to claim 1, wherein the solvent for dispersing the inorganic nanoparticles in step (b) is one or more selected from the group consisting of N, N-dimethylformamide, water, methanol and ethanol.
3. The method according to claim 1, wherein the Zr source and the H ligand are selected from the group consisting of Zr source, Zr ligand, and H ligand2The molar ratio of TCPP to the co-regulating ligand is (5-10): 1: (100-). sub.300.
4. The method according to claim 1, wherein in the step (c), the inorganic nanoparticle core is removed by etching the nanocomposite obtained in the step (b), acid etching is performed on the nanocomposite with cuprous oxide, ferroferric oxide, titanium dioxide, manganese oxide, aluminum oxide, zinc oxide, and calcium phosphate as the core, and alkaline etching or hydrofluoric acid etching is performed on the nanocomposite with silicon dioxide as the core.
5. The use of the material prepared by the preparation method of claim 1 in the preparation of a nano drug delivery system.
6. The use of claim 5, wherein the drug delivery system is for loading perfluorocarbons.
7. The use of claim 5, wherein the drug delivery nanosystem is used to support chemotherapeutic drugs, photothermal agents or imaging molecules.
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| CN112706170A (en) * | 2019-10-25 | 2021-04-27 | 湖南早晨纳米机器人有限公司 | Shell type nano robot and preparation method thereof |
| CN111514937B (en) * | 2020-05-13 | 2023-04-18 | 中国石油大学(华东) | Preparation method of porphyrin-based metal organic framework material sensitized oxide catalyst |
| CN113522363B (en) * | 2021-06-29 | 2022-11-15 | 北京科技大学 | Preparation method and application of metal ion modified MOF micro/nano structure in hydrogel |
| CN113831544B (en) * | 2021-09-22 | 2022-05-31 | 同济大学 | Non-linear nano hybrid material of titanium carbide quantum dots and vanadium metal organic framework and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013123517A1 (en) * | 2012-02-16 | 2013-08-22 | The Administrators Of The Tulane Educational Fund | Hollow nanoparticles with hybrid double layers |
| CN108517038A (en) * | 2018-03-15 | 2018-09-11 | 河南大学 | A kind of size regulation and control method of porphyrin metal organic framework material |
| CN108524934A (en) * | 2018-05-16 | 2018-09-14 | 武汉大学 | A kind of nano medicament carrying system and the preparation method and application thereof |
| JP2018176036A (en) * | 2017-04-07 | 2018-11-15 | 国立研究開発法人物質・材料研究機構 | Photocatalyst and method for using the same |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013123517A1 (en) * | 2012-02-16 | 2013-08-22 | The Administrators Of The Tulane Educational Fund | Hollow nanoparticles with hybrid double layers |
| JP2018176036A (en) * | 2017-04-07 | 2018-11-15 | 国立研究開発法人物質・材料研究機構 | Photocatalyst and method for using the same |
| CN108517038A (en) * | 2018-03-15 | 2018-09-11 | 河南大学 | A kind of size regulation and control method of porphyrin metal organic framework material |
| CN108524934A (en) * | 2018-05-16 | 2018-09-14 | 武汉大学 | A kind of nano medicament carrying system and the preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| High-performance electrocatalyst based on metal-organic framework/macroporous carbon composite for efficient detection of luteolin;Mengyuan Cao, et al;《Journal of Electroanalytical Chemistry》;20180727;第824卷;第153-160页 * |
| Zirconium-Porphyrin Based Metal-Organic Framework Hollow Nanotubes for Immobilization of Noble Metal Single Atoms;Ting He, et al;《Angewandte Chemie》;20180130;第57卷(第13期);第3493-3498页 * |
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