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CN-121673505-B - Copper porphyrin porous polymer with cavity inclusion and application thereof

CN121673505BCN 121673505 BCN121673505 BCN 121673505BCN-121673505-B

Abstract

The invention discloses a cuporphyrin porous polymer with a cavity inclusion and application thereof, and belongs to the technical field of biological medicines. The copper porphyrin porous polymer takes beta-cyclodextrin and a copper porphyrin complex as structural units, the copper porphyrin complex is combined with the beta-cyclodextrin through a covalent bond and surrounds the cyclodextrin, and the copper porphyrin complex around one cyclodextrin is not on the same plane. The 7-6-deoxy-6- (4-formylphenyl) -beta-cyclodextrin reacts with pyrrole through solvothermal reaction to obtain cyclodextrin porphyrin polymer, and the cyclodextrin porphyrin polymer reacts with copper salt to obtain copper coordination polymer. The cyclodextrin skeleton in the material provided by the invention provides abundant cavity inclusion capacity and high specific surface area, is favorable for adsorption and transmission of active species, and the copper coordination porphyrin unit formed by metal insertion modification contributes to excellent light absorption performance, high-efficiency photo-thermal conversion capability, stable singlet oxygen generation efficiency and Fenton-like catalytic activity.

Inventors

  • GAO FENG
  • Pang Shulan
  • LIN JIANHANG
  • XU DANDAN
  • ZHOU BAOLONG

Assignees

  • 山东第二医科大学

Dates

Publication Date
20260512
Application Date
20260209

Claims (8)

  1. 1. The copper porphyrin porous polymer with the cavity inclusion is characterized in that the copper porphyrin porous polymer takes beta-cyclodextrin and a copper porphyrin complex as structural units, the copper porphyrin complex is combined with the beta-cyclodextrin through a covalent bond and surrounds the cyclodextrin, and the copper porphyrin complex around one cyclodextrin is not on the same plane; The beta-cyclodextrin is 7-6-deoxy-6- (4-formylphenyl) -beta-cyclodextrin, and the porphyrin copper complex is porphin copper; the structural formula of the copper porphyrin porous polymer is as follows: 。
  2. 2. The cuporphyrin porous polymer according to claim 1, wherein said cuporphyrin porous polymer is prepared by the following method: (1) Dissolving 4-hydroxybenzaldehyde and potassium carbonate in DMF, performing room temperature reaction under a protective atmosphere, then dropwise adding a DMF solution of periodate-beta-cyclodextrin, heating for reaction, removing DMF under reduced pressure, cooling, filtering precipitate, recrystallizing to obtain white precipitate, washing and drying to obtain 7-6-deoxy-6- (4-formylphenyl) -beta-cyclodextrin; (2) Adding 7-6-deoxy-6- (4-formylphenyl) -beta-cyclodextrin into propionic acid, dropwise adding pyrrole under stirring in a protective atmosphere, and performing solvothermal reaction to obtain cyclodextrin porphyrin polymer; (3) Adding cyclodextrin porphyrin polymer and copper salt into absolute methanol, carrying out reflux reaction under a protective atmosphere, filtering, washing and drying after the reaction is finished to obtain the copper coordination polymer.
  3. 3. The cuporphyrin porous polymer according to claim 2, wherein in step (1), the molar ratio of 4-hydroxybenzaldehyde, potassium carbonate and periodate- β -cyclodextrin is 10:10:1, and the heating reaction is carried out at 80 ℃ for 24 hours.
  4. 4. The copper porphyrin porous polymer according to claim 2, wherein in the step (2), the molar ratio of the 7-6-deoxy-6- (4-formylphenyl) -beta-cyclodextrin to the pyrrole is less than or equal to 1:28, and the solvothermal reaction is carried out at a temperature of 140 ℃ for a time of 2d.
  5. 5. The copper porphyrin porous polymer according to claim 2, wherein in the step (3), the copper salt is copper acetate, the mass ratio of the cyclodextrin porphyrin polymer to the copper acetate is 2.17:1, and the reflux reaction is carried out at a temperature of 50 ℃ for 48 hours.
  6. 6. The use of a cuporphyrin porous polymer as claimed in any one of claims 1 to 5 in the preparation of antibacterial drugs.
  7. 7. The use according to claim 6, wherein said cuporphyrin porous polymer is antibacterial by mimicking photothermal, photodynamic, fenton action.
  8. 8. The use according to claim 7, wherein the photodynamic forces are type I photodynamic forces and type II photodynamic forces.

Description

Copper porphyrin porous polymer with cavity inclusion and application thereof Technical Field The invention relates to the technical field of biological medicines, in particular to a cuporphyrin porous polymer with a cavity inclusion and application thereof. Background In recent years, reactive Oxygen Species (ROS) -mediated catalytic therapeutic strategies have been of interest for their high selectivity, low susceptibility to drug resistance, and effective penetration into biological membranes. Among them, the combined application of photodynamic therapy (PDT), photothermal therapy (PTT) and chemo-kinetic therapy (CDT) has shown great potential. However, these therapies still face a number of bottlenecks in practical use, and single mode treatment often makes it difficult to completely clear the refractory biofilm. Porphyrin and derivatives ‌ thereof have both a photothermal effect and a photodynamic effect ‌, and the two characteristics enable the porphyrin and derivatives to have important application values in the field of phototherapy, in particular to antibacterial and antitumor treatment. Porphyrin is a planar macromolecular heterocyclic compound, and when porphyrin is polymerized, stacking is formed, and large pi bond planes between porphyrin and porphyrin overlap each other to generate pi-pi stacking effect. Pi-pi stacking can enhance non-radiative relaxation, reduce fluorescent radiation and the like, influence the photo-thermal conversion efficiency, close stacking can shield central metal ions, oxygen contact is blocked and the like, and the photo-dynamic efficiency is influenced. Therefore, the reasonable design of the polymer structure is needed to inhibit pi-pi accumulation, so that porphyrin has high-efficiency photo-thermal and photodynamic effects under specific conditions, and synergistic treatment is realized. Cyclodextrin has very good biocompatibility and a certain antibacterial effect, so reports of improving the antibacterial effect by polymerizing cyclodextrin and porphyrin gradually appear. The patent of application No. CN117327210A discloses a porphyrin micropore composite material based on beta-cyclodextrin terephthalaldehyde inclusion compound, a preparation method and application thereof, and the patent does not solve the problem of pi-pi accumulation of porphyrin although cyclodextrin and porphyrin are prepared into an antibacterial polymer. Compounds with a certain cavity structure, such as cyclodextrin, can be designed to enlarge the distance between porphyrin layers, so that pi-pi accumulation is avoided. Patent application number CN120173193a discloses a polyrotaxane covalent organic framework material and its use for controlling the interlayer spacing by cyclodextrin, which uses cyclodextrin to control the interlayer spacing, but uses gamma-cyclodextrin which is larger than the beta-cyclodextrin cavity to support the interlayer spacing. Patent application number CN121270877a discloses a macrocyclic covalent organic polymer material that suppresses pi-pi stacking effect and its use, using larger macrocyclic polymers to support the interlayer spacing. In the polymers of the two patents, porphyrin and porphyrin are still located on the same plane, and a compound with a large cavity structure is inserted into a planar structure such as porphyrin to avoid pi-pi accumulation. However, the beta-cyclodextrin has a smaller cavity structure, and it is difficult to suppress pi-pi accumulation by enlarging the interlayer spacing. Therefore, it is necessary to redesign a structure for beta-cyclodextrin and porphyrin, effectively inhibit pi-pi accumulation, and remarkably improve antibacterial effect through multi-mode antibacterial. Disclosure of Invention Aiming at the prior art, the invention aims to provide a cuporphyrin porous polymer with a cavity inclusion and application thereof. The invention constructs a conjugated polymer (Cu-CD-Por-COP) of porphyrin structural units based on beta-cyclodextrin and pyrrole, synchronously realizes the combination of pyrrole cyclization and macrocyclic porphyrin structure in the polymerization process of cyclodextrin derivatives containing seven acetal groups and pyrrole, and further endows the material with unique multifunctional synergistic characteristics that the cyclodextrin skeleton provides rich cavity inclusion capacity and high specific surface area, is beneficial to the adsorption and transmission of active species, and copper coordination porphyrin units formed by metal insertion modification contribute to excellent light absorption performance, high-efficiency photo-thermal conversion capacity, stable singlet oxygen generation efficiency and Fenton-like catalytic activity. In order to achieve the above purpose, the invention adopts the following technical scheme: In a first aspect of the present invention, there is provided a copper porphyrin porous polymer having cavities, wherein the copper porphyrin porous polymer takes beta-cyc