Porphyrin metal-organic framework (PMOF) material with hollow nanometer structure as well as preparation method and application thereof

A technology of metalloporphyrins and nanostructures, applied in the field of nanomaterials, can solve problems such as the decline of photodynamic curative effect, and achieve the effects of enhancing photodynamic effect, enhancing photodynamic therapy effect, excellent photocatalytic activity and photodynamic effect

Inactive Publication Date: 2019-03-29
WUHAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the hypoxic characteristics of most diseased tissues lead to a significant decline in photodynamic therapy. Moreover, photodynamic therapy is a process of rapid oxygen consumption, which causes a domino effect and further inhibits photodynamic therapy.

Method used

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  • Porphyrin metal-organic framework (PMOF) material with hollow nanometer structure as well as preparation method and application thereof
  • Porphyrin metal-organic framework (PMOF) material with hollow nanometer structure as well as preparation method and application thereof
  • Porphyrin metal-organic framework (PMOF) material with hollow nanometer structure as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] A preparation of a metalloporphyrin framework material with a hollow nanostructure, comprising the following steps:

[0040] (1) Add 0.001mol CuAc 2 ·3H 2 O and 0.01mol polyvinylpyrrolidone (PVP, MW30000) were dissolved in 30.0mL ethylene glycol. Then, 10.0 mL NaOH (2.0 mol·L -1 ), continue to stir for 0.5h, add 10.0mL ascorbic acid solution (0.3mol·L -1 ), followed by reaction at 55 °C for 30 min. After the product was collected by centrifugation, it was washed 3 times with water to obtain Cu 2 O nanoparticles.

[0041] (2) 10mg Cu 2 O nanoparticles were dispersed in 10mL DMF, and 0.093mmol ZrOCl was added 2 ·8H 2 O, 0.013 mmol H 2TCPP and 2.30mmol benzoic acid were heated at 90°C for 5h. After the reaction, cooled to room temperature, centrifuged to collect the product, and washed 3 times with DMF to obtain Cu 2 Nanocomposite Cu with O as the core and PMOF as the shell 2 O@PMOF.

[0042] (3) Cu 2 O@PMOF was dispersed in 50mL HCl (0.1mol L -1 ), stirred a...

Embodiment 2

[0048] A preparation of a metalloporphyrin framework material with a hollow nanostructure, comprising the following steps:

[0049] (1) Mix 74mL ethanol, 10mL H 2 O and 3.14 mL of ammonia solution were mixed and stirred at 30 °C for 0.5 h. Then, 6 mL 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 three times with ethanol and water respectively to obtain SiO 2 nanoparticles.

[0050] (2) Add 10mg SiO 2 Disperse in 10mL first-class water, add 10mL PVP (20mg·mL -1 ), stirred at room temperature for 12h, centrifuged to collect the product, and washed 3 times with primary water to obtain the SiO of surface-modified PVP 2 Nanoparticle SiO 2 @PVP.

[0051] (3) Add 10mg SiO 2 @PVP nanoparticles dispersed in 10mL DMF, add 0.093mmol ZrOCl 2 ·8H 2 O, 0.013 mmol H 2 TCPP and 2.3mmol benzoic acid were heated and reacted at 110°C for 5h. After the reaction, cool...

Embodiment 3

[0053] Example 3: Photodynamic effects of metalloporphyrin framework materials with hollow nanostructures loaded with perfluorohexane

[0054] The metalloporphyrin framework material (hollow PMOF) with a hollow nanostructure prepared in Example 1 of the present invention is used to load perfluorohexane (PFH) to obtain a hollow PMOF (PFH@hollow PMOF) loaded with perfluorohexane (PFH) , to verify the photodynamic effect. Taking hollow PMOF as a control, the operation steps are as follows:

[0055] (1) Fill 3mL hollow PMOF (10ug·mL -1 ) Add 15uLDPBF solution (10mol·L -1 ), 660nm laser (500mW·cm -2 ) was irradiated for different times, and UV-Vis was used to measure the change of the absorption value of 1,3-diphenylisobenzofuran (DPBF) at a wavelength of 467nm, and to measure the generation of singlet oxygen by the hollow PMOF. The results are as follows Figure 5 shown.

[0056] (2) To 3mLPFH@hollow PMOF (10ug·mL -1 ) Add 15uL DPBF solution (10mol·L -1 ), 660nm laser (500m...

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Abstract

The invention belongs to the field of nanometer materials, and relates to a porphyrin metal-organic framework (PMOF) with a hollow nanometer structure as well as a preparation method and application thereof. The material has a huge cavity and a casing, wherein the casing is made of the metalloporphyrin framework material. The size of the nanometer material is 20 to 200 nm; the casing layer thickness is 5 to 50 nm; the cavity diameter is 10 to 200 nm. The huge cavity of the hollow PMOF nano particles is used for loading perfluorocarbon; the perfluorocarbon has high oxygen dissolution performance; oxygen can be efficiently loaded; more oxygen is provided for photodynamics therapy, so that more singlet oxygen is generated; the photodynamic curative effect is enhanced. The huge cavity of the hollow PMOF nano particles and the casing layer pore can effectively load diagnostic reagents including chemotherapeutic drugs, optothermal reagents, imaging molecules and the like. The hollow PMOF haswide application prospects when being used as a novel nanometer drug carrier system.

Description

technical field [0001] The invention belongs to the field of nanomaterials, and in particular relates to a metalloporphyrin framework material with a hollow nanostructure and its preparation method and application. Background technique [0002] Metal-organic frameworks (MOFs) materials are a new type of organic-inorganic hybrid porous materials, which are composed of metal ions or metal cluster nodes and organic ligands. MOFs materials have excellent characteristics such as large specific surface area and porosity, adjustable pore size and shape controllable chemical structure and composition, and good biodegradability. Show great application potential. [0003] Porphyrin metal-organic frameworks (PMOF) is a three-dimensional stable and ordered spatial network structure formed by coordination of metal ions or metal ion clusters and photoactive carboxylate porphyrin ligands. The photosensitizer porphyrin molecule directly participates in the construction of PMOF as an organ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G83/00A61K41/00A61K47/34
CPCA61K41/0076A61K47/34C08G83/008
Inventor 田间徐华何桂华孙鑫
Owner WUHAN UNIV
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