Preparation method and antibacterial application of a porphyrin-based inorganic-organic composite

Abstract

The application belongs to the technical field of antibacterial materials, and provides a preparation method and antibacterial application of an inorganic-organic compound based on porphyrin, which is used for the treatment of wound infection. In the multifunctional antibacterial nano platform, ZIF-90@i-PPOP NPs encapsulated by an internal dynamic covalent hydrogel are composed, and have good drug controlled release effect. Once the wound is infected by microorganisms, the internal acid-sensitive hydrogel is degraded in the presence of bacterial acid secretion, which is beneficial to the release of ZIF-90@i-PPOP NPs, so as to exhibit excellent enzyme catalytic activity and Zn 2+ sustained release performance, which is beneficial to the removal of bacteria and the healing of the wound. The antibacterial experiment proves that the multifunctional hydrogel has excellent antibacterial activity and can effectively promote wound healing, and provides an inspiration for the development of a multi-modal antibacterial nano platform in the biomedical field.

Description

Technical Field

[0001] This invention belongs to the field of antibacterial materials technology, specifically relating to a method for preparing and applying an inorganic-organic complex based on porphyrin. Background Technology

[0002] The information disclosed in this background section is intended only to enhance understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] Bacterial infections have become a serious threat to human life and health. In the context of tissue growth, bacterial infections have a significant impact on individuals and communities, and severe infections can lead to chronic wound infections. While antibiotics can be used to combat bacterial infections, their misuse and overuse can lead to bacterial resistance. Some nanomaterials for combating drug-resistant bacteria have been used as alternatives to antibiotics, such as metal nanoparticles, metal oxides, and phototherapy agents. These materials primarily eliminate bacteria by generating reactive oxygen species (ROS), which mainly include singlet oxygen (ROS). 1 O2), superoxide anion (O 2- • and hydroxyl radicals (·OH). While these ROS-mediated antibacterial methods play a role in the sterilization process, single antibacterial properties are unlikely to achieve complete sterilization. Therefore, there is an urgent need to develop a method that can accelerate wound healing.

[0004] In recent years, with the rapid development of nanotechnology, advanced nanomedicines and nanoreagents have been designed, providing more opportunities for effective inflammation treatment and diverse biomedical applications. Among them, nanozymes, as a class of nanomaterials with high enzyme-like catalytic activity, have received unprecedented development and attention in regulating various biological processes. Artificial nanozymes, as substitutes for natural enzymes, overcome the inherent defects of natural enzymes such as poor stability, harsh reaction conditions, susceptibility to denaturation, and strict extraction requirements. However, due to the lack of active sites, nanozymes still differ significantly from natural enzymes in catalytic efficiency. Porphyrin-based porous organic polymers, especially transition metal porphyrin-based porous organic polymers, possess large specific surface areas and porous structures, endowed with sufficient catalytic active sites, providing a promising solution for improving enzyme-like catalytic capabilities. In recent years, various nanozyme catalysts have been reported to possess peroxidase-like activity, and are used in wound healing, treatment of microbial infections, degradation of environmental pollutants, and biosensing.

[0005] Ag + Cu 2+ Zn 2+Plasma possesses broad-spectrum antibacterial activity, directly disrupting biomolecules (proteins, lipids) on bacterial membranes, making it an effective sterilization method. Metal-organic frameworks (MOFs) are crystalline porous materials composed of metal ions / clusters and functionalized organic linkers, widely used in gas adsorption and separation, catalysis, drug delivery, and water treatment. Among them, ZIF-90 is considered a porous material with a large specific surface area and high loading capacity, exhibiting high biodegradability in acidic environments and releasing Zn. 2+ It exhibits significant antibacterial properties. Since the wound infection site is a slightly acidic environment, this will benefit the Zn content in ZIF-90. 2+ The slow release enhances the antibacterial effect.

[0006] Hydrogels, as wound dressings, possess superabsorbency, high load capacity, adjustable physical properties, and good biocompatibility, and have attracted increasing attention in the biomedical field in recent years. Many researchers have reported the great potential of three-dimensional hydrogels in wound healing and tissue remodeling. pH-sensitive hydrogels have been greatly encouraged in order to develop spatiotemporally controllable antibacterial strategies with minimal damage to normal tissue. Using formylphenylboronic acid as a bifunctional linker, an asymmetric building block, carboxymethyl chitosan, and tannic acid were combined to construct a dynamic covalent hydrogel with pH-responsive properties. More importantly, carboxymethyl chitosan, as a derivative of chitosan, exhibits good biocompatibility and water solubility, making it a promising candidate for use in wound dressings. Tannic acid possesses hemostatic and antioxidant properties, effectively stopping bleeding and scavenging excess reactive oxygen species generated by oxidative stress. Therefore, multifunctional hydrogels have become a practical tool for promoting wound healing.

[0007] However, the stability of the aforementioned multifunctional hydrogels still needs to be improved. Summary of the Invention

[0008] To address the aforementioned problems, this invention provides a novel multifunctional hydrogel for the treatment of wound infections. This multifunctional antibacterial nanoplatform comprises ZIF-90@i-PPOP NPs encapsulated in an internally dynamically covalent hydrogel, exhibiting excellent controlled drug release. Once the wound is infected by microorganisms, the internal acid-sensitive hydrogel degrades in the presence of bacterial secretions, facilitating the release of ZIF-90@i-PPOP NPs, thereby demonstrating superior enzymatic catalytic activity and Zn... 2+ The sustained-release properties facilitate bacterial clearance and wound healing. Antibacterial experiments have demonstrated that this multifunctional hydrogel possesses excellent antibacterial activity and can effectively promote wound healing, providing inspiration for the development of multimodal antibacterial nanoplatforms in the biomedical field.

[0009] To achieve the above objectives, the present invention adopts the following technical solution:

[0010] In a first aspect, the present invention provides a method for preparing an inorganic-organic complex based on porphyrin, comprising:

[0011] In the presence of a catalyst, ZIF-90 was reacted with an amino-containing metal porphyrin compound and an aldehyde-containing imidazole compound to obtain ZIF-90@i-PPOPs;

[0012] The ZIF-90@i-PPOPs were coated with a pH-responsive dynamic covalent hydrogel to obtain a biodegradable hydrogel, ZIF-90@i-PPOPs-Hydrogel.

[0013] In some embodiments, the amino-containing metalloporphyrin compound is 5,10,15,20-tetra(4-aminophenyl)ironporphyrin.

[0014] In some embodiments, the imidazole benzene compound containing an aldehyde group is 1,4-bis[1-(N-methyl-4-benzaldehyde)imidazolium]benzene.

[0015] In some embodiments, the catalyst is scandium trifluoromethanesulfonate.

[0016] In some embodiments, the mass ratio of ZIF-90 to 5,10,15,20-tetrakis(4-aminophenyl)ironporphyrin and 1,4-bis[1-(N-methyl-4-benzaldehyde)imidazolium]benzene is 40-80:45-90:73-160;

[0017] In some embodiments, the mass ratio of ZIF-90 to catalyst is 20:0.5 to 2.

[0018] In some embodiments, the pH-responsive dynamic covalent hydrogel is formed by combining carboxymethyl chitosan and tannic acid with formylphenylboronic acid as a bifunctional linker.

[0019] In some embodiments, the specific steps of the coating include: using formylphenylboronic acid as a bifunctional linker to combine ZIF-90@i-PPOPs, carboxymethyl chitosan and tannic acid.

[0020] In some embodiments, the mass ratio of tannic acid, 3-formylphenylboronic acid and ZIF-90@i-PPOPs is 85-150:104-208:4-8;

[0021] In some embodiments, the mass ratio of ZIF-90@i-PPOPs to carboxymethyl chitosan is 4–8:76–152.

[0022] In a second aspect, the present invention provides an inorganic-organic complex based on porphyrin prepared by the above-described method.

[0023] A third aspect of the present invention provides the application of the above-described porphyrin-based inorganic-organic complex in the preparation of wound dressings or antibacterial materials.

[0024] Beneficial effects of the present invention

[0025] (1) The multifunctional hydrogel of the present invention can be used for the treatment of wound infections. This multifunctional antibacterial nanoplatform consists of ZIF-90@i-PPOP NPs encapsulated in an internally dynamically covalent hydrogel, exhibiting excellent controlled drug release. Once the wound is infected by microorganisms, the internal acid-sensitive hydrogel is degraded in the presence of bacterial acidic secretions, which facilitates the release of ZIF-90@i-PPOP NPs, thereby demonstrating excellent enzyme catalytic activity and Zn... 2+ The sustained-release properties facilitate bacterial clearance and wound healing. Antibacterial experiments have demonstrated that this multifunctional hydrogel possesses excellent antibacterial activity and can effectively promote wound healing, providing inspiration for the development of multimodal antibacterial nanoplatforms in the biomedical field.

[0026] (2) The preparation method of the present invention is simple, practical and easy to promote. Attached Figure Description

[0027] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. Exemplary embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0028] Figure 1 The X-ray diffraction pattern of ZIF-90@i-PPOPs prepared in Example 2 of this invention.

[0029] Figure 2 The infrared spectrum of ZIF-90@i-PPOPs prepared in Example 2 of this invention;

[0030] Figure 3 The solid carbon spectrum of ZIF-90@i-PPOPs prepared in Example 2 of this invention;

[0031] Figure 4 Thermogravimetric analysis curve of ZIF-90@i-PPOPs prepared in Example 2 of this invention;

[0032] Figure 5 The image shows a scanning electron microscope (SEM) image of ZIF-90@i-PPOPs prepared in Example 2 of this invention.

[0033] Figure 6The following are rheological property characterization diagrams of ZIF-90@i-PPOPs-Hydrogel prepared in Example 4 of the present invention: A is a scanning electron microscope image of ZIF-90@i-PPOPs-Hydrogel; B is a stress scanning image of ZIF-90@i-PPOPs-Hydrogel; and C is a dynamic stress scanning image of ZIF-90@i-PPOPs-Hydrogel.

[0034] Figure 7 The image shows the antibacterial activity of ZIF-90@i-PPOPs prepared in Example 2 of this invention; where A is the antibacterial activity against Staphylococcus aureus and B is the antibacterial activity against Escherichia coli.

[0035] Figure 8 The images show SEM images of Staphylococcus aureus and Escherichia coli treated with ZIF-90@i-PPOPs prepared in Example 2 of this invention. A and B are Staphylococcus aureus, and C and D are Escherichia coli.

[0036] Figure 9 The ZIF-90@i-PPOPs-Hydrogel prepared in Example 4 of this invention was used to construct a mouse back wound model; I was the control group, II was the ZIF-90-Hydrogel group, III was the i-PPOPs-Hydrogel group, and IV was the ZIF-90@i-PPOPs-Hydrogel group. Detailed Implementation

[0037] It should be noted that the following detailed descriptions are exemplary and intended to provide further illustration of the invention. Unless otherwise specified, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0038] The present invention will be further described in detail below with reference to specific embodiments. It should be noted that the specific embodiments are explanations of the present invention and not limitations thereof.

[0039] In the following examples, the ZIF-90 nanoparticles are prepared as follows:

[0040] Zinc nitrate hexahydrate (123.8 mg) was dissolved in a mixture of tert-butanol (3.3 mL) and H₂O (3.3 mL). Then, a mixture of glycerol (3.3 mL) and H₂O (3.3 mL) containing polyvinylpyrrolidone (16.7 mg) and 4-imidazolium carboxaldehyde (10 mg) was added dropwise to the above solution. The mixture was stirred at room temperature for 10 minutes. Subsequently, the synthesized ZIF-90 nanoparticles were collected by centrifugation, washed three times with ethanol, and freeze-dried under vacuum to obtain a white solid.

[0041] The synthetic method of 5,10,15,20-tetra(4-aminophenyl)ironporphyrin is as follows:

[0042] 5,10,15,20-tetra(4-aminophenyl)porphyrin and anhydrous ferric chloride (32.44 mg) were added to 30 mL of anhydrous N,N-dimethylformamide to prepare 5,10,15,20-tetra(4-aminophenyl)ferroporphyrin under nitrogen protection. After stirring at 165 °C for 4 h, N,N-dimethylformamide was distilled off under reduced pressure. The resulting solid was subjected to silica gel column chromatography with dichloroethane / methanol [10:1 (v / v)] as the eluent. The crude product was purified by recrystallization from CH2Cl2 / MeOH to obtain deep purple 5,10,15,20-tetra(4-aminophenyl)ferroporphyrin.

[0043] Example 1

[0044] The preparation method of i-PPOPs is as follows:

[0045] Under nitrogen protection, triimidazole benzene (22.5 mg) and p-bromomethylbenzaldehyde (895 mg) were reacted in 5 mL of N,N-dimethylformamide at 80 °C for 24 hours. After cooling to room temperature, the solid was filtered and washed three times with ethanol to obtain 1,4-bis[1-(N-methyl-4-benzaldehyde)imidazole]benzene.

[0046] 5,10,15,20-Tetra(4-aminophenyl)iron porphyrin (22.5 mg) and 1,4-bis[1-(N-methyl-4-benzaldehyde)imidazolium]benzene (36.5 mg) were continuously sonicated for 10 min at room temperature. Then, 1 mL of scandium trifluoromethanesulfonate (1 mg / mL) was added dropwise to the mixture to replace the protic acid as a catalyst for the reaction of 5,10,15,20-tetra(4-aminophenyl)iron porphyrin with 1,4-bis[1-(N-methyl-4-benzaldehyde)imidazolium]benzene, and the mixture was continuously sonicated for 10 min. The synthesized i-PPOPs were collected by centrifugation, washed with N,N-dimethylformamide and acetone, and then freeze-dried under vacuum.

[0047] Example 2

[0048] The preparation method of ZIF-90@i-PPOPs is as follows:

[0049] First, ZIF-90 (20 mg) was ultrasonically dispersed in N,N-dimethylformamide (5 mL) for 10 min. Then, 5,10,15,20-tetra(4-aminophenyl)iron porphyrin (22.5 mg) and 1,4-bis[1-(N-methyl-4-benzaldehyde)imidazolium]benzene (36.5 mg) were added, and the mixture was continuously sonicated for 10 min at room temperature. Next, 1 mL of scandium trifluoromethanesulfonate (1 mg / mL) was added dropwise to the mixture to replace the protic acid to catalyze the reaction of 5,10,15,20-tetra(4-aminophenyl)iron porphyrin with 1,4-bis[1-(N-methyl-4-benzaldehyde)imidazolium]benzene, and the mixture was continuously sonicated for 10 min. The synthesized ZIF-90@i-PPOPs were collected by centrifugation, washed with N,N-dimethylformamide and acetone, and then freeze-dried under vacuum.

[0050] Example 3

[0051] Synthesis of biodegradable hydrogels:

[0052] Tannic acid (85 mg) and 3-formylphenylboronic acid (104 mg) were mixed in 2 mL of aqueous solution with constant stirring. The pH of the mixture was adjusted to 8.2 with sodium hydroxide solution (1 M). Then, carboxymethyl chitosan (76 mg) dissolved in 2 mL of water was added to the mixture and stirred for 2 min. After standing at room temperature for 5 min, a biodegradable hydrogel was synthesized.

[0053] Example 4

[0054] Synthesis of ZIF-90@i-PPOPs-Hydrogel.

[0055] Tannic acid (85 mg), 3-formylphenylboronic acid (104 mg), and ZIF-90@i-PPOPs (4 mg) prepared in Example 2 were mixed in 2 mL of aqueous solution with constant stirring. The pH of the mixture was adjusted to 8.2 with NaOH solution (1 M). Then, carboxymethyl chitosan (76 mg) dissolved in 2 mL of water was added to the above mixture and stirred for 2 min. After standing at room temperature for 5 min, the biodegradable hydrogel ZIF-90@i-PPOPs-Hydrogel was synthesized.

[0056] Experimental Example 1

[0057] Culture of Staphylococcus aureus:

[0058] Staphylococcus aureus and Escherichia coli were cultured separately in bacterial culture medium for 12 hours, and the bacteria were collected by centrifugation and then diluted with PBS. Finally, the bacteria were diluted to 1×10⁻⁶ using the 600 nm densitometer method. 6CFU / mL. To investigate the antibacterial activity of ZIF-90, i-PPOPs, and ZIF-90@i-PPOPs, two typical Gram-positive bacteria (Staphylococcus aureus) and Gram-negative bacteria (Escherichia coli) were selected for the study. Specifically, different concentrations of ZIF-90, i-PPOPs, and ZIF-90@i-PPOPs (8, 16, 32, 64, 128, 256 μg / mL) were co-cultured with Staphylococcus aureus and Escherichia coli, respectively.

[0059] Experimental Example 2

[0060] Material characterization:

[0061] like Figure 1 As shown, the crystal structures of the synthesized ZIF-90 and ZIF-90@i-PPOPs were determined by X-ray diffraction. The diffraction peaks of the synthesized ZIF-90@i-PPOPs appeared at 2Θ of 7.35, 10.54, 12.94, 14.68, 16.62, 18.24, 22.30, 24.56 and 26.82, corresponding to the simulated lattice planes (011), (200), (112), (022), (013), (222), (114), (233) and (134).

[0062] like Figure 2 As shown, ZIF-90@i-PPOPs were characterized using infrared spectroscopy. The 955 cm⁻¹ of ZIF-90... -1 1678cm -1 and 2853cm -1 The characteristic peaks at 1618 cm⁻¹ originate from Zn-N, C=O, and CH bonds in ICA, and these characteristic peaks are retained in ZIF-90@i-PPOPs, indicating the successful synthesis of ZIF-90@i-PPOPs. Furthermore, at 1618 cm⁻¹... -1 The characteristic peak at that location is attributed to the C=N stretching vibration generated by the bond between 5,10,15,20-tetra(4-aminophenyl)porphyrin iron and 1,4-bis[1-(N-methyl-4-benzaldehyde)imidazolium]benzene.

[0063] like Figure 3 As shown, ZIF-90@i-PPOPs were characterized using solid-state carbon NMR spectroscopy. The peaks of approximately 119 to 150 ppm are attributed to aromatic carbon atoms in ZIF-90@i-PPOPs. Furthermore, the signal of 160.6 ppm corresponds to the carbon atom of the imine bond, indicating that 5,10,15,20-tetra(4-aminophenyl)porphyrin iron and 1,4-bis[1-(N-methyl-4-benzaldehyde)imidazolium]benzene have been successfully integrated into the framework.

[0064] Based on the results of X-ray diffraction, infrared spectroscopy, and solid-state carbon NMR spectroscopy, the successful preparation of ZIF-90@i-PPOPs can be confirmed.

[0065] like Figure 4 As shown, the thermal stability of ZIF-90@i-PPOPs was characterized by thermogravimetric analysis (TGA). The results show that ZIF-90@i-PPOPs has good heat resistance. Under the protection of N2, the weight loss rate is less than 10% when the temperature reaches 100℃. Such high stability ensures that ZIF-90@i-PPOPs can withstand harsh environmental conditions.

[0066] like Figure 5 As shown, the morphological characteristics of ZIF-90@i-PPOPs were characterized by scanning electron microscopy. ZIF-90@i-PPOPs exhibit a dodecahedral structure with a rough surface and abundant surface catalytic sites.

[0067] like Figure 6 As shown in Figure A, the morphology and rheological properties of the hydrogel were determined using scanning electron microscopy and rheology analysis, respectively. The hydrogel exhibits a rich porous structure, which is beneficial for the delivery of antibacterial agents. In the stress scanning test, the storage modulus (G′) of ZIF-90@i-PPOPs-Hydrogel was higher than the loss modulus (G″), indicating the successful preparation of the hydrogel. The critical point between the solid-liquid state and the hydrogel was 200% strain. Dynamic strain tests were conducted at 1% and 500% pressures to evaluate the self-healing ability of the hydrogel. The experimental results show that the hydrogel has excellent self-healing ability.

[0068] like Figure 7 As shown, Staphylococcus aureus (S. aureus) was selected respectively. Figure 7 (A) and Escherichia coli ( Figure 7 B) represents typical Gram-positive and Gram-negative bacteria. ZIF-90 and i-PPOPs+H2O2 were used as control groups to investigate their antibacterial activity. First, the antibacterial performance of the three groups was explored using OD600 values. It can be seen that the antibacterial efficiency is positively correlated with the concentration of ZIF-90@i-PPOPs. When the concentration of ZIF-90@i-PPOPs increased from 8 μg / mL to 128 μg / mL in the presence of H2O2, the antibacterial efficiencies against Staphylococcus aureus and Escherichia coli increased from 2.7% and 3.3% to 77.3% and 76.5%, respectively. Further increasing the concentration of ZIF-90@i-PPOPs to 256 μg / mL resulted in inhibition rates of 100% and 99.9%, respectively. Figure 7 China A and Figure 7In the B group, at the corresponding concentrations, ZIF-90 showed antibacterial activities of 36.2% and 24.1% against Staphylococcus aureus and Escherichia coli, respectively, and antibacterial activities of 42.6% and 40.3% against i-PPOPs+H2O2, respectively.

[0069] like Figure 8 As shown in the figure, the SEM images of Staphylococcus aureus and Escherichia coli treated with ZIF-90@i-PPOPs are prepared in this embodiment of the invention, wherein A and B are Staphylococcus aureus, and C and D are Escherichia coli.

[0070] Figure 9 The ZIF-90@i-PPOPs-Hydrogel prepared for this embodiment of the invention was used to construct a mouse back wound model; I was the control group, II was the ZIF-90-Hydrogel group, III was the i-PPOPs-Hydrogel group, and IV was the ZIF-90@i-PPOPs-Hydrogel group.

[0071] from Figure 9 As can be seen, on the first day of wound infection, all groups showed varying degrees of suppuration, proving that the back wounds were successfully infected with Staphylococcus aureus. The infected wounds were then treated with ZIF-90-Hydrogel, i-PPOPs-Hydrogel, and ZIF-90@i-PPOPs-Hydrogel, respectively. The wounds treated with ZIF-90-Hydrogel and i-PPOPs-Hydrogel showed a slight increase in size on day 4, while the wounds treated with ZIF-90@i-PPOPs-Hydrogel healed faster on day 7 than the other groups, and were completely healed by day 10.

[0072] Therefore, this invention, composed of ZIF-90@i-PPOP NPs encapsulated in an internally dynamic covalent hydrogel, exhibits excellent controlled drug release. Once the wound is infected by microorganisms, the internal acid-sensitive hydrogel degrades in the presence of bacterial secretions, facilitating the release of ZIF-90@i-PPOP NPs and thus promoting Zn release. 2+ The sustained release and the enzymatic properties of i-PPOP NPs work synergistically to achieve efficient bacterial clearance and promote wound healing.

[0073] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for producing a porphyrin-based inorganic-organic composite, characterized by, include: In the presence of a catalyst, ZIF-90 is reacted with an amino-containing metalloporphyrin compound and an aldehyde-containing imidazole compound to obtain ZIF-90@i-PPOPs; the amino-containing metalloporphyrin compound is 5,10,15,20-tetra(4-aminophenyl)ironporphyrin; the aldehyde-containing imidazole compound is 1,4-bis[1-(N-methyl-4-benzaldehyde)imidazolium]benzene; and the catalyst is scandium trifluoromethanesulfonate. The ZIF-90@i-PPOPs were coated with a pH-responsive dynamic covalent hydrogel to obtain a biodegradable hydrogel, ZIF-90@i-PPOPs-Hydrogel.

2. The method for producing a porphyrin-based inorganic-organic composite according to claim 1, characterized by, The mass ratio of ZIF-90 to 5,10,15,20-tetrakis(4-aminophenyl)ironporphyrin and 1,4-bis[1-(N-methyl-4-benzaldehyde)imidazolium]benzene is 40~80:45~90:73~160; Alternatively, the mass ratio of ZIF-90 to catalyst is 20:0.5~2.

3. The method for producing a porphyrin-based inorganic-organic composite according to claim 1, wherein The pH-responsive dynamic covalent hydrogel is composed of carboxymethyl chitosan and tannic acid, with formylphenylboronic acid as a bifunctional linker.

4. The method for producing a porphyrin-based inorganic-organic composite according to Claim 1, wherein The specific steps of the coating include: using formylphenylboronic acid as a bifunctional linker to combine ZIF-90@i-PPOPs, carboxymethyl chitosan and tannic acid.

5. The method for producing a porphyrin-based inorganic-organic composite according to claim 4, wherein The mass ratio of tannic acid, formylphenylboronic acid and ZIF-90@i-PPOPs is 85~150:104~208:4~8; Alternatively, the mass ratio of ZIF-90@i-PPOPs to carboxymethyl chitosan is 4~8:76~152.

6. The porphyrin-based inorganic-organic complex prepared by the method of any one of claims 1-5.

7. The application of the porphyrin-based inorganic-organic complex of claim 6 in the preparation of wound dressings or antibacterial materials.

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