Spherical phosphorus-containing porphyrin COF antibacterial material as well as preparation method and application thereof

Abstract

The invention discloses a spherical phosphorus-containing porphyrin COF antibacterial material and a preparation method and application thereof, and belongs to the field of functional material preparation, the material is of a spherical structure, the diameter is 100-300 nm, and the photothermal conversion efficiency is 53.84%. The preparation method comprises the following steps: firstly, synthesizing amino porphyrin from p-nitrobenzaldehyde and pyrrole through a solvothermal method, and preparing a phosphorus-containing compound from vanillin and phenyl dichlorophosphate through a solvothermal method; finally, amino porphyrin and a phosphorus-containing compound are combined through a Schiff base reaction, and the spherical phosphorus-containing porphyrin COF antibacterial material is successfully prepared. According to the powder material, the bacterium eradication rates of staphylococcus aureus and escherichia coli can reach 99.35% and 99.72% respectively through the photothermal-photodynamic synergistic effect. In addition, the spherical phosphorus-containing porphyrin COF antibacterial material disclosed by the invention can also improve the mechanical, flame-retardant and antibacterial properties of poly-eutectic solvent gel, and has a wide application prospect.

Description

Technical Field

[0001] The present invention relates to the field of functional material preparation, in particular to a spherical phosphorus-containing porphyrin COF antibacterial material and a preparation method and application thereof. Background Art

[0002] Bacterial infections pose a serious threat to human health, especially the growing problem of drug-resistant strains of Staphylococcus aureus and Escherichia coli due to overuse of antibiotics. Over the past 70 years of antibiotic use, overuse has led to a continuous increase in bacterial resistance, significantly reducing the clinical efficacy of traditional antibiotics. There is an urgent need to develop novel, non-antibiotic-dependent antimicrobial strategies.

[0003] In recent years, the combination of nanotechnology and photoresponsive therapy has provided a new direction for the field of antibacterial therapy. Photothermal therapy (PTT) converts light energy into heat energy through photothermal agents, and uses high temperature to destroy bacterial cell membranes and biomacromolecules to achieve sterilization, while photodynamic therapy (PDT) relies on photosensitizers to produce reactive oxygen species (ROS) under light, which damages key components of bacteria through oxidation. Both have the advantage of not inducing drug resistance and show the potential to replace antibiotics. For example, Chinese patent CN118217395A discloses selenium-doped gold-silver bimetallic nanoparticles, whose near-infrared photothermal responsiveness can quickly heat up and sterilize, but the material still has limitations in biocompatibility and long-term stability, and a single photothermal mechanism may lead to insufficient antibacterial efficiency.

[0004] At the same time, the development of carrier materials is crucial to improving antibacterial efficacy. Gels, due to their three-dimensional network structure and tunable physical and chemical properties, are ideal carriers for drug delivery and wound repair. Porphyrin-based nanomaterials have attracted considerable attention due to their excellent photodynamic properties and biocompatibility. However, existing technologies often face the problem of decreased photosensitivity due to aggregation, and their composite methods with the gel matrix are mostly limited to physical mixing, making it difficult to achieve functional synergy. Summary of the Invention

[0005] In view of the shortcomings of the existing technology, the purpose of the present invention is to provide a spherical phosphorus-containing porphyrin COF antibacterial material to solve the existing problems.

[0006] In order to achieve the above object, the technical solution of the present invention is as follows:

[0007] Spherical phosphorus-containing porphyrin COF antibacterial material, the antibacterial material includes aminoporphyrin and phosphorus-containing compound, the antibacterial material has a spherical structure, the diameter of the antibacterial material is 100-300nm, and the structural formula of the antibacterial material is:

[0008]

[0009] A method for preparing a spherical phosphorus-containing porphyrin COF antibacterial material, the preparation method comprising the following steps:

[0010] S1, synthesizing aminoporphyrin from nitrobenzaldehyde and pyrrole;

[0011] S2, synthesizing a phosphorus-containing compound from vanillin and phenyl dichloride phosphate;

[0012] S3. Aminoporphyrin is combined with a phosphorus-containing compound through a Schiff base reaction to prepare a spherical phosphorus-containing porphyrin COF antibacterial material.

[0013] Furthermore, the S1 is specifically:

[0014] S1.1, using p-nitrobenzaldehyde and pyrrole as raw materials, performing a condensation reaction to obtain nitroporphyrin powder;

[0015] S1.2. Using nitroporphyrin and hydrochloric acid as raw materials, a nitro reduction reaction is carried out to obtain aminoporphyrin powder.

[0016] Furthermore, the S2 specifically comprises: using vanillin and phenyl dichloride phosphate as raw materials, performing a substitution reaction to obtain a phosphorus-containing compound.

[0017] Furthermore, the step S3 specifically comprises: adding the TAPP powder obtained in S1 and the phosphorus-containing compound obtained in S2 to an ethanol solution at a molar ratio of 1:2-4, and the nanopowder precipitate obtained after the reaction is a spherical phosphorus-containing porphyrin COF antibacterial material.

[0018] Furthermore, the S1.1 is specifically as follows:

[0019] S1.1.1. Under nitrogen, dissolve p-nitrobenzaldehyde in a mixture of propionic acid and propionic anhydride and stir at room temperature for 30 min.

[0020] S1.1.2. Slowly add the mixed solution of pyrrole and propionic anhydride to the mixed solvent in S1.1.1 through a constant pressure dropping funnel and react at 120-150°C for 3 hours;

[0021] S1.1.3. After the reaction is completed, cool naturally to room temperature, collect the precipitate of the solution in S1.1.2 by suction filtration, and wash the precipitate thoroughly with methanol;

[0022] S1.1.4. Dry the precipitate in a forced air drying oven at 100°C and grind the dried product into fine powder. Add pyridine to the ground precipitate and stir at 70°C for 30 minutes to finally obtain nitroporphyrin.

[0023] Furthermore, the S1.2 is specifically as follows:

[0024] S1.2.1. Under nitrogen, stir and mix nitroporphyrin, hydrochloric acid, and tin chloride dissolved in hydrochloric acid at room temperature for 2-3 hours; then react at 70-80°C for 30-40 minutes;

[0025] S1.2.2. After the reaction is completed, cool to room temperature and slowly add aqueous ammonia to the mixture in S1.2.1 to make the mixture weakly alkaline.

[0026] S1.2.3. Extract the mixture of S1.2.2 with DMF and dichloromethane. The obtained extract solution is further purified by rotary evaporation to finally obtain aminoporphyrin.

[0027] Furthermore, the S2 is specifically:

[0028] Add vanillin, triethylamine, anhydrous potassium carbonate, tetrabutylammonium bromide and tetrahydrofuran into a three-necked flask, stir and introduce nitrogen at room temperature;

[0029] After 10-15 minutes of reaction, slowly add a mixture of phenyl dichloride phosphate and tetrahydrofuran to the three-necked flask dropwise. Set the reaction temperature to 60-80°C, continue stirring and react for 6-8 hours, and then cool to room temperature.

[0030] Obtaining a filtrate under vacuum filtration, and subjecting the filtrate to rotary evaporation to obtain a crude product of the phosphorus-containing compound;

[0031] The crude product was treated by column chromatography using ethyl acetate:petroleum ether = 1:2 as eluent, and the solvent was completely removed under reduced pressure to obtain a yellow oily phosphorus-containing compound.

[0032] Furthermore, the S3 is specifically:

[0033] S3.1. Add aminoporphyrin, mesitylene, and acetic acid to a reaction kettle and stir for 10-30 minutes;

[0034] S3.2. Add the mixture of phosphorus-containing compound and anhydrous ethanol dropwise to the reactor and continue stirring for 15-30 minutes;

[0035] S3.3. Place the reaction solution from S3.2 in a 120°C air drying oven, react for 12-16 hours, and cool to room temperature.

[0036] S3.4. Wash the dried product obtained by centrifugation in S3.3 with ethanol and dry it in a forced air drying oven to obtain a spherical phosphorus-containing porphyrin COF antibacterial material.

[0037] Application of spherical phosphorus-containing porphyrin COF antibacterial materials, which are used in the preparation of PDES gel to improve the working performance of PDES gel, including antibacterial performance, tensile stress, toughness and flame retardancy;

[0038] The preparation method comprises the following steps:

[0039] The spherical phosphorus-containing porphyrin COF antibacterial material was placed in the DES solution and stirred to prepare a P-Por COF / DES suspension;

[0040] Add the photoinitiator to the P-Por COF / DES suspension, stir until uniform, and then add it to the polytetrafluoroethylene mold;

[0041] The polytetrafluoroethylene mold was irradiated with a UV curing machine to allow the suspension to undergo in-situ polymerization to obtain a P-Por COF / PDES gel.

[0042] Compared with the prior art, the present invention has the following beneficial effects:

[0043] 1) The spherical phosphorus-containing porphyrin COF antibacterial material prepared by the present invention is formed by the Schiff base reaction of TAPP and a phosphorus-containing compound, has a spherical morphology, and has a large specific surface area.

[0044] 2) The spherical phosphorus-containing porphyrin COF antibacterial material prepared by the present invention has good biocompatibility, the near-infrared light used has spatial controllability and strong penetrating ability, and causes little damage to the human body.

[0045] 3) The spherical phosphorus-containing porphyrin COF antibacterial material prepared by the present invention can generate singlet oxygen to further kill bacteria on the basis of destroying the cell structure by generating heat under light.

[0046] 4) The spherical phosphorus-containing porphyrin COF antimicrobial material prepared in this invention can be combined with a poly (deep eutectic solvent) (PDES) gel to form a composite gel. This composite gel not only inherits the antimicrobial ability of the spherical phosphorus-containing porphyrin COF antimicrobial material, but also improves the tensile strain, tensile strength, toughness, and flame retardancy of the PDES gel. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0048] Figure 1 1H NMR spectrum (a) of TAPP prepared in Example 1 and 1H NMR spectrum (b) and 31P NMR spectrum (c) of the P-containing compound.

[0049] Figure 2These are scanning electron micrographs (Figures ab) of the spherical phosphorus-containing porphyrin COF antibacterial material prepared in Example 1 and transmission electron micrographs (Figures cd) of the spherical phosphorus-containing porphyrin COF antibacterial material.

[0050] Figure 3 These are Fourier infrared spectra of the aminoporphyrin (TAPP), phosphorus-containing compound and spherical phosphorus-containing porphyrin COF antibacterial material prepared in Example 1.

[0051] Figure 4 This is the X-ray diffraction analysis (XRD) of the spherical phosphorus-containing porphyrin COF antibacterial material prepared in Example 1.

[0052] Figure 5 This is the X-ray photoelectron spectroscopy (XPS) of the spherical phosphorus-containing porphyrin COF antibacterial material prepared in Example 1.

[0053] Figure 6 This is the thermogravimetric analysis (TGA) of the spherical phosphorus-containing porphyrin COF antibacterial material prepared in Example 1.

[0054] Figure 7 This is the degradation curve of the ultraviolet-visible light absorption of the spherical phosphorus-containing porphyrin COF antibacterial material prepared in Example 1 dispersed in DPBF ethanol solution over time.

[0055] Figure 8 This is a data graph of infrared thermal imaging and time-temperature changes of the spherical phosphorus-containing porphyrin COF antibacterial material prepared in Example 1 dispersed in an aqueous solution.

[0056] Figure 9 The sterilization plate diagram and plate count statistics diagram of the spherical phosphorus-containing porphyrin COF antibacterial material prepared in Example 1 (ab: Staphylococcus aureus; cd: Escherichia coli).

[0057] Figure 10 Scanning electron micrographs of bacteria treated with the spherical phosphorus-containing porphyrin COF antibacterial material prepared in Example 1 (ab: Escherichia coli; cd: Staphylococcus aureus);

[0058] Figure 11 The P-Por COF / PDES gel sterilization plate image and plate count statistics (ab: Staphylococcus aureus; cd: Escherichia coli) prepared in the present invention. DETAILED DESCRIPTION

[0059] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention are clearly and completely described. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0060] The present invention provides a spherical phosphorus-containing porphyrin COF antibacterial material. This spherical phosphorus-containing porphyrin COF antibacterial material is characterized by a novel nanomaterial prepared by a Schiff base reaction of 5,10,15,20-tetrakis(4-aminophenyl)porphyrin and a phosphorus-containing compound. This nanomaterial has a spherical structure with a diameter of 100-300 nm and a photothermal conversion efficiency of 53.84% under 730 nm near-infrared light. Its structural formula is shown below.

[0061]

[0062] Example 1

[0063] Preparation of spherical phosphorus-containing porphyrin COF antibacterial materials:

[0064] 1) Dissolve 7.6 g of p-nitrobenzaldehyde in a mixture of 100 mL of propionic acid and 35 mL of propionic anhydride and stir at room temperature under a nitrogen atmosphere for 30 minutes. Subsequently, a mixture of pyrrole and propionic anhydride (4.7 mL of pyrrole and 10 mL of propionic anhydride) was slowly added dropwise via a constant pressure dropping funnel and reacted at 150°C for 3 hours. After the reaction, the mixture was cooled to room temperature, the precipitate was collected by filtration, and washed thoroughly with methanol. The crude product was dried in a forced air drying oven at 100°C and ground into a fine powder. An appropriate amount of pyridine was added to remove the pyrrole polymer (stirring at 70°C for 30 minutes), yielding 5,10,15,20-tetrakis(4-nitrophenyl)porphyrin (TNPP).

[0065] 2) TNPP (1.8 g) obtained in step 1) was stirred at room temperature for 2 hours under a nitrogen atmosphere, along with 75 mL of hydrochloric acid and 7 g of tin chloride (dissolved in 20 mL of hydrochloric acid). The mixture was then reacted at 70°C for 30 minutes. After the reaction was complete and cooled to room temperature, aqueous ammonia was slowly added dropwise until the mixture became weakly alkaline. The mixture was then extracted with DMF and dichloromethane. The resulting solution was further purified by rotary evaporation to yield 5,10,15,20-tetrakis(4-aminophenyl)porphyrin (TAPP).

[0066] 3) Vanillin (21.63 g), triethylamine (20 mL), anhydrous potassium carbonate (19.65 g), tetrabutylammonium bromide (0.51 g), and tetrahydrofuran (250 mL) were added to a three-necked flask and stirred while purging with nitrogen at room temperature. After 10 minutes, a mixture of phenyl dichlorophosphate (10 g) and tetrahydrofuran (50 mL) was slowly added dropwise to the three-necked flask. The reaction temperature was set to 60°C, and stirring was continued for 6 hours before cooling to room temperature. The filtrate was vacuum filtered and rotary evaporated to obtain the crude phosphorus-containing compound. Finally, the crude product was purified by column chromatography (ethyl acetate:petroleum ether = 1:2 as eluent) and the solvent was completely removed under reduced pressure to obtain the phosphorus-containing compound as a yellow oil (yield: 60%).

[0067] 4) The aminoporphyrin (TAPP, 135 mg) obtained in step 2) was added to a reaction vessel along with mesitylene (10 mL) and acetic acid (6 mol / L, 2 mL) and stirred for 10 minutes. A mixture of the phosphorus-containing compound (266 mg) obtained in step 3) and anhydrous ethanol (10 mL) was then added dropwise to the reaction vessel and stirred for 30 minutes. The mixture was then placed in a 120°C air drying oven for 12 hours and cooled to room temperature. The product was washed with ethanol, centrifuged (8500 rpm), and dried in an air drying oven to obtain a spherical phosphorus-containing porphyrin COF antibacterial material.

[0068] Figure 1 The 1H NMR spectrum (a) of the aminoporphyrin (TAPP) prepared in Example 1, the 1H NMR spectrum (b), and the 31P NMR spectrum (c) of the phosphorus-containing compound are shown. The singlet at a chemical shift of 8.894 ppm corresponds to hydrogen atoms on the porphyrin ring, the doublet at chemical shifts of 7.871 and 7.851 ppm and the doublet at 7.018 and 6.997 ppm correspond to hydrogen atoms on the benzene ring, and the singlets at chemical shifts of 5.574 and 2.013 ppm correspond to pyrrole NH and -NH2, respectively. The hydrogen atoms on the benzene ring of the phosphorus-containing compound are located at 7.398-7.540 ppm, and the singlets at chemical shifts of 9.933 and 3.827 ppm correspond to hydrogen atoms on the aldehyde group and methyl group, respectively.

[0069] Figure 2 Scanning electron micrographs (a) and (b) of the spherical phosphorus-containing porphyrin COF antibacterial material prepared in Example 1 show that the spherical phosphorus-containing porphyrin COF antibacterial material exhibits a regular spherical structure with a smooth surface. Transmission electron micrographs (c) and (d) of the spherical phosphorus-containing porphyrin COF antibacterial material show that the diameter of the spherical phosphorus-containing porphyrin COF antibacterial material ranges from 100 to 300 nm, confirming the successful synthesis of the spherical phosphorus-containing porphyrin COF antibacterial material nanocomposite.

[0070] Figure 3 This is a Fourier transform infrared spectrum of the spherical phosphorus-containing porphyrin COF antibacterial material prepared in Example 1. As can be seen from the figure, the NH bond on the aminoporphyrin (3336 cm-1) and the C=O bond on the phosphorus-containing compound (1692 cm-1) are visible. The disappearance of the C=O bond on the spherical phosphorus-containing porphyrin COF antibacterial material also confirms the synthesis of the spherical phosphorus-containing porphyrin COF antibacterial material.

[0071] Figure 4 This is the X-ray diffraction analysis (XRD) of the spherical phosphorus-containing porphyrin COF antibacterial material prepared in Example 1. P-PorCOF shows obvious peaks at 21.46° and 43.68°, further confirming the successful synthesis of P-Por COF.

[0072] Figure 5 This is the X-ray photoelectron spectroscopy (XPS) of the spherical phosphorus-containing porphyrin COF antibacterial material prepared in Example 1. The figure shows a wide scan of the spherical phosphorus-containing porphyrin COF antibacterial material, with signals for P 2p, N 1s, C 1s, and O 1s observed (Figure a). The corresponding high-resolution C 1s spectrum of the spherical phosphorus-containing porphyrin COF antibacterial material (Figure b) displays four peaks at 284.88, 285.68, 286.68, and 287.68 eV, corresponding to C-C (C=C), CN (CO), C=N, and C-H bonds, respectively. The N 1s XPS spectrum (Figure c) can be divided into two types of N species (C=N and CN), while the O 1s XPS spectrum (Figure d) can be divided into three types of O species (CO, OH, and PO).

[0073] Figure 6 This is a thermogravimetric analysis (TGA) of the spherical phosphorus-containing porphyrin COF antibacterial material prepared in Example 1. The figure shows that the initial decomposition temperature (T-5%) of the P-Por COF is 270°C, and that 80.2% and 62.3% of the original mass are retained at 400°C and 800°C, respectively, demonstrating that the P-Por COF has good thermal stability and carbonization rate.

[0074] Figure 7 This is a UV-visible light absorption graph of a DPBF solution of the spherical phosphorus-containing porphyrin COF antibacterial material prepared in Example 1 after illumination. The graph clearly shows that the DPBF absorbance curve shows almost no significant change. Compared to Figure a, the absorbance at 415 nm is significantly reduced after the addition of the spherical phosphorus-containing porphyrin COF antibacterial material (Figure b), and the DPBF absorption decay rate of the spherical phosphorus-containing porphyrin COF antibacterial material reaches 53.86% from 0 min to 10 min. This indicates that the spherical phosphorus-containing porphyrin COF antibacterial material has the ability to generate singlet oxygen. Figure c provides a visual summary of the decrease in absorbance at 415 nm for DPBF and P-Por COF+DPBF.

[0075] Figure 8 The infrared thermal imaging and time-temperature data of the spherical phosphorus-containing porphyrin COF antibacterial material prepared in Example 1 dispersed in an aqueous solution are shown. As can be seen from the figure, under 730nm laser irradiation (400mW / cm2), the temperature of the spherical phosphorus-containing porphyrin COF antibacterial material aqueous solution with a concentration of 200μg / mL rose from 29.9°C to 65.5°C within 4 minutes, with a total increase of ΔT = 35.6°C (Figure a). As shown in Figure b, the absorbance of the spherical phosphorus-containing porphyrin COF antibacterial material is related to its concentration. The results show that even at low concentrations, the sample can still display a relatively broad absorption spectrum in the wavelength range of 300-900nm. In addition, during the six cycles when the laser irradiation was turned off, the spherical phosphorus-containing porphyrin COF antibacterial material exhibited good photostability (Figure c). Then, the fitting straight line of Figure d was obtained based on the cooling part of a cycle in Figure c, and then the slope of the fitting straight line was obtained. Finally, according to the photothermal conversion formula, the photothermal conversion efficiency of the spherical phosphorus-containing porphyrin COF antibacterial material at 730nm was calculated to be 53.84%.

[0076] Example 2

[0077] Preparation of spherical phosphorus-containing porphyrin COF antibacterial materials:

[0078] 1) Dissolve 7.6 g of p-nitrobenzaldehyde in a mixture of 125 mL of propionic acid and 50 mL of propionic anhydride and stir at room temperature under a nitrogen atmosphere for 30 minutes. Subsequently, a mixture of pyrrole and propionic anhydride (6 mL of pyrrole and 25 mL of propionic anhydride) was slowly added dropwise via a constant pressure dropping funnel and reacted at 120°C for 3 hours. After the reaction, the mixture was cooled to room temperature, the precipitate was collected by filtration, and washed thoroughly with methanol. The crude product was dried in a forced air drying oven at 100°C and ground into a fine powder. An appropriate amount of pyridine was added to remove the pyrrole polymer (stirring at 70°C for 30 minutes), yielding 5,10,15,20-tetrakis(4-nitrophenyl)porphyrin (TNPP).

[0079] 2) TNPP (1.8 g) obtained in step 1), 75 mL of hydrochloric acid, and 7 g of tin chloride (dissolved in 20 mL of hydrochloric acid) were stirred at room temperature under a nitrogen atmosphere for 3 hours, followed by reaction at 80°C for 40 minutes. After the reaction was complete and cooled to room temperature, aqueous ammonia was slowly added dropwise until the mixture became weakly alkaline. The mixture was then extracted with DMF and dichloromethane. The resulting solution was further purified by rotary evaporation to obtain 5,10,15,20-tetrakis(4-aminophenyl)porphyrin (TAPP).

[0080] 3) Vanillin (21.63 g), triethylamine (20 mL), anhydrous potassium carbonate (19.65 g), tetrabutylammonium bromide (0.51 g), and tetrahydrofuran (200 mL) were added to a three-necked flask and stirred while purging with nitrogen at room temperature. After 15 minutes, a mixture of phenyl dichlorophosphate (10 g) and tetrahydrofuran (50 mL) was slowly added dropwise to the three-necked flask. The reaction temperature was set to 80°C, and stirring was continued for 8 hours before cooling to room temperature. The filtrate was vacuum filtered and rotary evaporated to obtain the crude phosphorus-containing compound. Finally, the crude product was purified by column chromatography (ethyl acetate:petroleum ether = 1:2 as eluent) and the solvent was completely removed under reduced pressure to obtain the phosphorus-containing compound as a yellow oil (yield: 60%).

[0081] 4) The aminoporphyrin (TAPP, 135 mg) obtained in step 2) was added to a reaction vessel along with mesitylene (10 mL) and acetic acid (6 mol / L, 2 mL) and stirred for 30 minutes. A mixture of the phosphorus-containing compound (178 mg) obtained in step 3) and anhydrous ethanol (10 mL) was then added dropwise to the reaction vessel and stirred for 15 minutes. The mixture was then placed in a 120°C air drying oven for 16 hours and cooled to room temperature. The spherical phosphorus-containing porphyrin COF antibacterial material was obtained by washing with ethanol, centrifuging (6000 rpm), and drying in an air drying oven.

[0082] Antibacterial ability test of spherical phosphorus-containing porphyrin COF antibacterial material:

[0083] The spherical phosphorus-containing porphyrin COF antibacterial material prepared in Example 1 was dispersed in the broth used for bacterial culture at concentrations of 0, 100, and 200 μg·mL⁻¹. The suspension was irradiated with a 730 nm laser at 2 W·cm⁻² for 6 minutes, incubated at 37°C for 4 hours, and diluted 10,000-fold with phosphate buffer. 100 μL of the diluted suspension was applied to Luria Bertani solid culture medium and incubated in a 37°C incubator for 16 hours. Images of the colonies formed after treatment were obtained, and bacterial counts were performed to calculate the bactericidal efficiency.

[0084] Table 1

[0085]

[0086]

[0087] Table 1 shows the bacterial survival rate data of Escherichia coli and Staphylococcus aureus measured by plate count method under different concentrations (0, 100, 200 μg·mL-1) of spherical phosphorus-containing porphyrin COF antibacterial material with or without NIR irradiation (808 nm, 2 W·cm-2, 6 min).

[0088] The bactericidal effect of the spherical phosphorus-containing porphyrin COF antibacterial material prepared in Example 1 was shown in the image of the plate count method. Figure 9 The results showed that the antibacterial properties of the spherical phosphorus-containing porphyrin COF antibacterial material improved with increasing concentration. At a concentration of 200 μg·mL⁻¹, it demonstrated a 99.72% sterilization rate against Escherichia coli and over 99.35% against Staphylococcus aureus. Comparison of the results between the two bacteria revealed that photothermal sterilization was more effective against E. coli than against Staphylococcus aureus, due to differences in cell wall composition between Gram-negative and Gram-positive bacteria.

[0089] The bacterial samples were observed by SEM. Figure 10 As shown in Figures a and c, without laser treatment, Staphylococcus aureus and Escherichia coli are round and plump, with clear edges and smooth surfaces. However, with laser treatment, the bacterial surfaces become rough and concave, and even cellular contents leak out, ultimately leading to bacterial death. Therefore, P-PorCOF primarily destroys the bacterial cell membrane and cell wall through thermal calcination, disrupting the bacteria's normal physiological functions and ultimately causing bacterial death. The bacterial sample pretreatment is as follows: First, the sample to be tested is dispersed in an ethanol solution and subjected to ultrasound-assisted dispersion to obtain a uniformly dispersed suspension. Subsequently, the sample suspension is evenly coated onto the surface of a clean silicon wafer substrate using a capillary method and allowed to dry naturally at room temperature. Bacterial samples require fixation before preparation. An equal volume of 2.5% glutaraldehyde solution is added to the laser-irradiated bacterial broth to fix the bacteria overnight. Bacterial samples are then centrifuged (5000 rpm, 5 minutes) with ethanol solutions of 30%, 50%, 70%, 90%, and 100% by volume, respectively.

[0090] Application Examples

[0091] The present invention first prepares a P-Por COF / PDES composite gel through a reasonable preparation process. The composite gel has excellent mechanical properties and outstanding photothermal conversion efficiency, and has a good bactericidal effect at relatively low concentrations. Bacteria can be inactivated in a short time, and the bactericidal rate can reach more than 99%.

[0092] Specific application implementation

[0093] The preparation method of the spherical phosphorus-containing porphyrin COF antibacterial material combined with the poly-eutectic solvent gel composite material of the present invention and its mechanical and antibacterial properties are further described in detail below with reference to the examples and drawings.

[0094] Preparation of PDES gel: Acrylic acid (25 g) and choline chloride (25.7 g) were added to a single-necked flask at a molar ratio of 1:2, sealed with a glass stopper, and stirred at 90°C for 3 h to form a transparent, slightly viscous DES solution. Photoinitiator I2959 (8 mg) was added to the DES solution (5 g), stirred thoroughly, and poured into a polytetrafluoroethylene mold. The mixture was irradiated with a UV curing device (wavelength 365 nm, 72 mW / cm2) for 30 s to initiate in-situ polymerization, yielding a PDES elastomer.

[0095] Preparation of the P-Por COF / PDES composite gel: 1.25 mg of spherical phosphorus-containing porphyrin COF antimicrobial material was placed in a DES (5 g) solution and stirred for 20 minutes until a homogeneous solution was obtained. Photoinitiator I2959 (8 mg) was then added to the P-PorCOF / DES suspension and stirred until uniform. The suspension was then placed in a polytetrafluoroethylene mold and irradiated with a UV curing device (wavelength 365 nm, 72 mW / cm2) for 30 seconds to initiate in-situ polymerization, resulting in a P-Por COF / PDES composite gel (mass fraction 0.025%).

[0096] Antibacterial ability test of P-Por COF / PDES composite gel:

[0097] First, 50 μL of glycerol-preserved Escherichia coli and Staphylococcus aureus were added to 50 mL of LB broth, shaken, and placed in a 37°C constant temperature shaker for 8 hours and 30 minutes to obtain a bacterial solution containing 1×109 CFU per milliliter. 5 μL of the bacterial solution was dropped onto different gels and irradiated with NIR light or left untreated (denoted as L+ and L-, respectively). The gels were then rinsed with 5 mL of sterile deionized water and diluted 30-fold. 100 μL of the co-culture solution was placed on LB agar medium, shaken, and placed in a 37°C constant temperature incubator for 16 hours. The cells were then counted using the agar plate method.

[0098] The P-Por COF / PDES composite gel and PDES gel were subjected to thermogravimetric analysis, antibacterial performance test, tensile performance test, and micro-combustion calorimeter test, and the relevant data are shown in Table 2. Compared with PDES gel, the mechanical properties of P-PorCOF / PDES gel with 0.025wt% added were improved in terms of tensile stress and strain. When the content of P-Por COF increased from 0wt% to 0.025wt%, the tensile strain increased from 1481% to 2436%, and the tensile stress increased from 0.28MPa to 0.54MPa. It is worth noting that the toughness of P-Por COF / PDES gel reached 8.66MJ / m3, which is about 2.6 times the toughness of PDES (3.310.03MJ / m3). And by comparing the peak heat release rate and total heat release of the samples in Example 1 and Example 2, it can be seen that the flame retardant properties of PDES gel with the addition of P-Por COF are better.

[0099] Table 2

[0100]

[0101] Figure 11 Images of the plate count method for the bactericidal efficacy of the prepared P-Por COF / PDES gel. The results show that the antibacterial properties of the P-Por COF / PDES gel increase with increasing concentration. At a concentration of 0.025wt%, the gel demonstrated a 99.992% bactericidal rate against Escherichia coli and over 99.989% against Staphylococcus aureus. Comparing the results of the two bacterial tests revealed that photothermal sterilization was more effective against E. coli than against S. aureus, due to differences in cell wall composition between Gram-negative and Gram-positive bacteria.

[0102] In summary, the spherical phosphorus-containing porphyrin COF antibacterial material of the present invention can improve the mechanical, flame retardant and antibacterial properties of poly(deep eutectic solvent) gel (PDES), indicating that it is a multifunctional additive that can enhance the comprehensive properties of polymer materials and has broad application prospects.

[0103] It should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply the existence of any such actual relationship or order between these entities or operations. Moreover, the terms "comprises," "comprising," or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article, or device comprising a series of elements includes not only those elements, but also other elements not explicitly listed, or elements inherent to such process, method, article, or device. In the absence of further limitations, an element defined by the phrase "comprising a ..." does not exclude the presence of other identical elements in the process, method, article, or device comprising the element.

[0104] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. Spherical phosphorus-containing porphyrin COF antibacterial material, characterized by: The antibacterial material includes aminoporphyrin and phosphorus-containing compounds. The antibacterial material has a spherical structure with a diameter of 100-300nm. The structural formula of the antibacterial material is:

2. A method for preparing a spherical phosphorus-containing porphyrin COF antibacterial material, characterized by: The preparation method comprises the following steps: S1, synthesizing aminoporphyrin from nitrobenzaldehyde and pyrrole; S2, synthesizing a phosphorus-containing compound from vanillin and phenyl dichloride phosphate; S3. Aminoporphyrin is combined with a phosphorus-containing compound through a Schiff base reaction to prepare a spherical phosphorus-containing porphyrin COF antibacterial material.

3. The method for preparing the spherical phosphorus-containing porphyrin COF antibacterial material according to claim 2, characterized in that: The specific S1 is: S1.1, using p-nitrobenzaldehyde and pyrrole as raw materials, performing a condensation reaction to obtain nitroporphyrin powder; S1.

2. Using nitroporphyrin and hydrochloric acid as raw materials, a nitro reduction reaction is carried out to obtain aminoporphyrin powder.

4. The method for preparing the spherical phosphorus-containing porphyrin COF antibacterial material according to claim 2, wherein: Specifically, S2 is as follows: using vanillin and phenyl dichloride phosphate as raw materials, performing a substitution reaction to obtain a phosphorus-containing compound.

5. The method for preparing the spherical phosphorus-containing porphyrin COF antibacterial material according to claim 2, characterized in that: Specifically, S3 is as follows: adding the TAPP powder obtained in S1 and the phosphorus-containing compound obtained in S2 to an ethanol solution at a molar ratio of 1:2-4, and the nanopowder precipitate obtained after the reaction is a spherical phosphorus-containing porphyrin COF antibacterial material.

6. The method for preparing the spherical phosphorus-containing porphyrin COF antibacterial material according to claim 3, characterized in that: The S1.1 specifically includes: S1.1.

1. Under nitrogen, dissolve p-nitrobenzaldehyde in a mixture of propionic acid and propionic anhydride and stir at room temperature for 30 min. S1.1.

2. Slowly add the mixed solution of pyrrole and propionic anhydride to the mixed solvent in S1.1.1 through a constant pressure dropping funnel and react at 120-150°C for 3 hours; S1.1.

3. After the reaction is completed, cool naturally to room temperature, collect the precipitate of the solution in S1.1.2 by suction filtration, and wash the precipitate thoroughly with methanol; S1.1.

4. Dry the precipitate in a forced air drying oven at 100°C and grind the dried product into fine powder. Add pyridine to the ground precipitate and stir at 70°C for 30 minutes to finally obtain nitroporphyrin.

7. The method for preparing the spherical phosphorus-containing porphyrin COF antibacterial material according to claim 6, characterized in that: The specific details of S1.2 are: S1.2.

1. Under nitrogen, stir and mix nitroporphyrin, hydrochloric acid, and tin chloride dissolved in hydrochloric acid at room temperature for 2-3 hours; then react at 70-80°C for 30-40 minutes; S1.2.

2. After the reaction is completed, cool to room temperature and slowly add aqueous ammonia to the mixture in S1.2.1 to make the mixture weakly alkaline. S1.2.

3. Extract the mixture of S1.2.2 with DMF and dichloromethane. The obtained extract solution is further purified by rotary evaporation to finally obtain aminoporphyrin.

8. The method for preparing the spherical phosphorus-containing porphyrin COF antibacterial material according to claim 4, characterized in that: The specific S2 is: Add vanillin, triethylamine, anhydrous potassium carbonate, tetrabutylammonium bromide and tetrahydrofuran into a three-necked flask, stir and introduce nitrogen at room temperature; After 10-15 minutes of reaction, slowly add a mixture of phenyl dichloride phosphate and tetrahydrofuran to the three-necked flask dropwise. Set the reaction temperature to 60-80°C, continue stirring and react for 6-8 hours, and then cool to room temperature. Obtaining a filtrate under vacuum filtration, and subjecting the filtrate to rotary evaporation to obtain a crude product of the phosphorus-containing compound; The crude product was treated by column chromatography using ethyl acetate:petroleum ether = 1:2 as eluent, and the solvent was completely removed under reduced pressure to obtain a yellow oily phosphorus-containing compound.

9. The method for preparing the spherical phosphorus-containing porphyrin COF antibacterial material according to claim 5, characterized in that: The specific S3 is: S3.

1. Add aminoporphyrin, mesitylene, and acetic acid to a reaction kettle and stir for 10-30 minutes; S3.

2. Add the mixture of phosphorus-containing compound and anhydrous ethanol dropwise to the reactor and continue stirring for 15-30 minutes; S3.

3. Place the reaction solution from S3.2 in a 120°C air drying oven, react for 12-16 hours, and cool to room temperature. S3.

4. Wash the dried product obtained by centrifugation in S3.3 with ethanol and dry it in a forced air drying oven to obtain a spherical phosphorus-containing porphyrin COF antibacterial material.

10. Application of spherical phosphorus-containing porphyrin COF antibacterial material, characterized by: The antibacterial material is used in the preparation of PDES gel to improve the working performance of PDES gel, including antibacterial performance, tensile stress, toughness and flame retardancy; The preparation method comprises the following steps: The spherical phosphorus-containing porphyrin COF antibacterial material was placed in the DES solution and stirred to prepare a P-Por COF / DES suspension; Add the photoinitiator to the P-Por COF / DES suspension, stir until uniform, and then add it to the polytetrafluoroethylene mold; The polytetrafluoroethylene mold was irradiated with a UV curing machine to allow the suspension to undergo in-situ polymerization to obtain a P-Por COF / PDES gel.

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