Porphyrin-based covalent organic framework nano material, preparation method and application of porphyrin-based covalent organic framework nano material in polyurethane

Abstract

The invention discloses a porphyrin-based covalent organic framework nano material, a preparation method and application of the porphyrin-based covalent organic framework nano material in polyurethane, and belongs to the field of functional nano materials and antibacterial materials. The porphyrinyl covalent organic framework nano material is prepared from 5, 10, 15, 20-tetra (4-aminophenyl) porphyrin and bis-(5-formyl furfuryl) ether through a Schiff base reaction, and the structural formula of the porphyrinyl covalent organic framework nano material is # imgabs0. The porphyrinyl covalent organic framework nano material prepared by the invention has relatively high photothermal conversion efficiency when being used as a photothermal agent, and has a relatively good sterilization effect under the condition of relatively low concentration. Besides, based on the porphyrin-based covalent organic framework nano material, a WPUS / Por-COF composite film is prepared, the composite film has excellent mechanical properties and excellent photothermal conversion efficiency, and has a good sterilization effect under the condition of relatively low concentration, bacteria can be inactivated within a short time, and the sterilization rate can reach 99% or above.

Description

Technical Field

[0001] The present invention belongs to the field of functional nanomaterials and antibacterial materials, and particularly relates to a porphyrin-based covalent organic framework nanomaterial, a preparation method and application thereof in polyurethane. Background Art

[0002] Pathogen infections pose a major threat to the environment, food, and public health. In particular, potential contamination accidents caused by foodborne pathogens pose a threat to public health. Foodborne pathogens pose a huge threat to humans through the environment and food chain, leading to poisoning or infectious diseases. Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli), as typical foodborne pathogens, can form biofilms on biological and non-biological surfaces, leading to food contamination and spoilage. In order to minimize the harm caused to humans by these foodborne pathogens, effective antimicrobial drugs and methods are needed. Traditionally, antibiotics have been used to control microbial contamination, but overuse can lead to increased drug resistance and loss of efficacy. Therefore, it is necessary to find efficient and safe alternative antimicrobial disinfection technologies.

[0003] In recent years, advances in nanotechnology have driven the exploration of innovative nanoplatforms for the treatment of serious diseases. Among them, photodynamic therapy (PDT) and photothermal therapy (PTT) are noteworthy. Photothermal therapy is a method of using light irradiation to activate a photothermal agent, converting the light absorbed by the photothermal agent into heat, thereby causing bacterial death by destroying cell membrane structure and denaturing proteins. In addition, photothermal therapy does not cause the development of drug-resistant bacteria, so it is effective against superbugs. Photodynamic therapy (PDT) has attracted great attention in the treatment of bacterial infections due to its non-invasiveness, negligible side effects, broad-spectrum antibacterial properties, and potential to overcome drug resistance. Under laser irradiation, the photosensitizer (PS) absorbs light energy and converts it into O2, which then produces reactive oxygen species (ROS). ROS can destroy bacteria by destroying biomacromolecules such as phospholipids, enzymes, proteins, and DNA. Chinese patent CN118217395 A reports a selenium-doped gold-silver bimetallic nanoparticle that has a rapid photothermal temperature rise response under near-infrared light irradiation. Chinese patent CN 114209826 A reports the preparation and application of zinc porphyrin nanoparticles, which can effectively generate singlet oxygen and convert photons into heat energy under light of a specific wavelength, giving the particles excellent drug-loading capacity and enabling combined PDT and PTT therapy.

[0004] The present invention attempts to prepare porphyrin-based covalent organic framework nanomaterials and apply them to photothermal / photodynamic synergistic antibacterial therapy, hoping to exert their excellent bactericidal properties. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a porphyrin-based covalent organic framework nanomaterial, a preparation method and application thereof in polyurethane.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is:

[0007] A porphyrin-based covalent organic framework nanomaterial, whose structural formula is shown below, is spherical in structure with a diameter of 400-600 nm and a photothermal conversion efficiency of 77% under 730 nm near-infrared light.

[0008]

[0009] The present invention also proposes a preparation method of a porphyrin-based covalent organic framework nanomaterial. First, p-nitrobenzaldehyde and pyrrole are used as raw materials to undergo a condensation reaction to obtain 5,10,15,20-alkyl(4-nitrophenyl)porphyrin (TNPP); then, under heating conditions, the nitro group of TNPP is subjected to an oxidation-reduction reaction using anhydrous stannous chloride and dilute hydrochloric acid to obtain 5,10,15,20-tetrakis(4-aminophenyl)porphyrin (TAPP); finally, 5,10,15,20-tetrakis(4-aminophenyl)porphyrin (TAPP) and bis-(5-formylfurfuryl) ether (OBMF) are subjected to a Schiff base condensation reaction under high temperature conditions to obtain a porphyrin-based covalent organic framework nanomaterial (Por-COF).

[0010] Furthermore, the preparation method of the porphyrin-based covalent organic framework nanomaterial comprises the following steps:

[0011] 1) First, p-nitrobenzaldehyde is used as the raw material, propionic acid and propionic anhydride are added, nitrogen is passed through the mixture at room temperature, magnetic stirring is performed, and pyrrole is added dropwise to react to obtain TNPP;

[0012] 2) Using TNPP as a raw material, anhydrous stannous chloride and dilute hydrochloric acid are added to carry out a redox reaction. After the reaction is completed, the mixture is cooled to room temperature and ammonia is added to adjust the pH value to a weak alkaline state. The mixture is extracted with DMF and dichloromethane to obtain TAPP;

[0013] 3) TAPP, OBMF, 1,3,5-trimethylbenzene, and glacial acetic acid were poured into a high-temperature reactor, and anhydrous ethanol was added dropwise with magnetic stirring to produce Por-COF by a Schiff base condensation reaction under a solvothermal method.

[0014] As a further preferred technical solution of the present invention, the specific steps of preparing TNPP in step 1) of the preparation method are as follows: adding the raw material p-nitrobenzaldehyde (7.6 g) to propionic acid (100 mL) and propionic anhydride (35 mL) and passing N2 protection at room temperature, magnetically stirring for 30 minutes, adding pyrrole (4.7 mL dissolved in 10 mL propionic anhydride) dropwise to the solution using a separatory funnel, reacting at 150°C for 3 hours (N2 protection), cooling and reflux, cooling to room temperature, filtering to obtain a precipitate, washing with methanol, and then drying in an oven at 100°C; grinding the crude product into a solid powder with a mortar and pouring it into a three-necked flask, heating to 70°C, while slowly adding pyridine dropwise, continuing magnetic stirring for 30 minutes, then terminating the reaction, washing with propionic acid, and collecting the solid (TNPP).

[0015] As a further preferred technical solution of the present invention, the specific steps of preparing TAPP in step 2) of the preparation method are: 1.8 g TNPP, 75 mL HCl, and 7 g SnCl2 (dissolved in 20 mL HCl) are mixed under nitrogen flow, magnetically stirred at room temperature for 2 hours, and then heated in an oil bath at 70°C for 0.5 hours; after the reaction is completed, the mixture is cooled to room temperature and ammonia water is added to adjust the pH to a weak alkaline value; extraction is carried out with DMF and dichloromethane, and further purification is performed by rotary evaporation to obtain the TAPP product.

[0016] As a further preferred technical solution of the present invention, the specific steps of preparing Por-COF in step 3) of the preparation method are: first pour TAPP (135 mg), 1,3,5-trimethylbenzene (10 mL), and glacial acetic acid (6 mol / L, 2 mL) into a high-temperature reactor container, add anhydrous ethanol dropwise and magnetically stir for 10 minutes, then add OBMF (242 mg) and stir for 5 minutes; then place the high-temperature reactor in an oven at 120°C and react for 12 hours; obtain a purple precipitate, centrifuge it with anhydrous ethanol (5000 r / min) to neutralize it, and place it in an oven to dry to obtain the product Por-COF.

[0017] The present invention firstly prepares a porphyrin-based covalent organic framework nanomaterial through a reasonable preparation process. As a photothermal agent, it has a high photothermal conversion efficiency and a good bactericidal effect at a relatively low concentration. When the Por-COF concentration is 150 μg·mL -1 It can be used in NIR (730nm, 2W·cm -2 , 6min) under light to raise the temperature, bacteria can be inactivated in a short time, and the sterilization rate can reach more than 99%. In addition, based on the above-mentioned porphyrin-based covalent organic framework nanomaterial, the present invention first prepared a WPUS through a reasonable preparation process. 1.5 / Por-COF-Xwt% composite film, which has excellent mechanical properties and outstanding light-to-heat conversion efficiency, and has a good bactericidal effect at relatively low concentrations. Bacteria can be inactivated in a short time, and the sterilization rate can reach more than 99%. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 (a) Synthesis route and (b) H NMR spectrum of TAPP prepared in Example 1.

[0019] Figure 2 This is the synthetic route of Por-COF prepared in Example 1.

[0020] Figure 3 This is the SEM image of Por-COF prepared in Example 1.

[0021] Figure 4 TEM image of Por-COF prepared in Example 1.

[0022] Figure 5 This is the infrared spectrum of Por-COF prepared in Example 1.

[0023] Figure 6 XPS spectrum (a) and high-resolution C 1s, N 1s, and O 1s XPS spectra (bd) of Por-COF prepared in Example 1.

[0024] Figure 7 PXRD spectrum of Por-COF prepared in Example 1, as well as simulated PXRD and its difference (a) and AA stacking unit cell and side view of AA stacking (b).

[0025] Figure 8 The Por-COF prepared in Example 1 was exposed to 730 nm laser (20 mW / cm 2 ) Absorption spectrum of DPBF solution after irradiation (a), absorption spectrum of DPBF+Por-COF solution (b) and absorption spectrum of Por-COF generated 1 Time-dependent degradation curve of DPBF by O2 (c).

[0026] Figure 9 The Por-COF solution prepared in Example 1 at different concentrations and deionized water were detected at 730 nm (2 W / cm 2 ) Temperature rise curve under laser irradiation (a) and Por-COF (150 μg / mL) at 730 nm (2 W / cm 2 ) Five heating and cooling cycle curves under laser irradiation and infrared thermal imaging of the heating process (b-c).

[0027] Figure 10 Images showing the bactericidal effect of the exfoliated Por-COF prepared in Example 1 using plate counts. (ab) Photographs of S. aureus and E. coli cultured on agar plates after treatment with different concentrations of Por-COF; (cd) Statistical analysis of bacterial viability based on the number of colonies grown on agar plates after treatment with different concentrations of Por-COF (Mean ± SD, n = 3).

[0028] Figure 11 Bio-based waterborne polyurethane (WPUS) prepared in Application Example 1 and Application Example 2 1.5 ) and WPUS 1.5 Mechanical properties curve of / Por-COF-Xwt% composite film.

[0029] Figure 12 WPUS prepared in Application Example 2 1.5 / Por-COF-Xwt% composite film in the dark and near infrared 730nm (2W / cm 2 ) Staphylococcus aureus and Escherichia coli were infected with WPUS with different Por-COF contents under laser irradiation. 1.5 Photographs of cultures on agar plates after film treatment (ab) and the growth of Staphylococcus aureus and Escherichia coli after being cultured on WPUS containing different Por-COF contents 1.5 The number of colonies cultured on the agar plate after film treatment was used for statistical analysis of bacterial activity (cd) (Mean±SD, n=3). DETAILED DESCRIPTION

[0030] The present invention is further described in detail below with reference to the embodiments and drawings.

[0031] Preparation Example:

[0032] Example 1

[0033] Preparation of porphyrin-based covalent organic frameworks:

[0034] 1) Add p-nitrobenzaldehyde (7.6 g) to propionic acid (150 mL) and propionic anhydride (35 mL) at room temperature under N2 protection. Stir magnetically for 30 minutes. Add pyrrole (4.7 mL dissolved in 15 mL propionic anhydride) dropwise to the solution using a separatory funnel. React at 150°C for 3 hours (under N2 protection). Cool to reflux. After cooling to room temperature, filter the precipitate, rinse three times with methanol, and then dry in an oven at 100°C. Grind the crude product into a solid powder in a mortar and pestle, pour it into a three-necked flask, heat to 70°C, and slowly add pyridine dropwise. Continue magnetic stirring for 30 minutes. Then terminate the reaction, wash with propionic acid, and collect the solid (TNPP).

[0035] 2) 1.8 g TNPP, 75 mL HCl, and 7 g SnCl2 (dissolved in 20 mL HCl) were mixed under N2 flow and magnetically stirred at room temperature for 2 h. The mixture was then heated in an oil bath at 70°C for 0.5 h. After the reaction was complete, the mixture was cooled to room temperature and the pH was adjusted to a weakly alkaline state by adding aqueous ammonia. The product TAPP was extracted with DMF and dichloromethane and further purified by rotary evaporation.

[0036] 3) First, pour TAPP (135 mg), 1,3,5-trimethylbenzene (10 mL), and glacial acetic acid (6 mol / L, 2 mL) into a high-temperature reactor. Add anhydrous ethanol dropwise and stir magnetically for 10 minutes. Then add OBMF (242 mg) and stir for 5 minutes. Then, place the high-temperature reactor in an oven at 120°C for 12 hours. The resulting purple precipitate was centrifuged with anhydrous ethanol (5000 rpm) to neutralize the solution and dried in an oven until ready for use.

[0037] Figure 1 The synthetic route (a) and H NMR spectrum (b) of TAPP prepared in Example 1. 1 The chemical structure of TAPP was characterized by H NMR. Figure 1 As can be seen in (b), the peak at -2.72 ppm (s, 2H) is attributed to the pyrrole nitrogen hydrogen, the peak at 5.58 ppm (s, 8H) corresponds to the hydrogen on the amino functional group, and the peaks at 7.03 ppm (s, 8H) and 7.86 ppm (m, 8H) are -CH- peaks on the benzene ring. In addition, a -CH peak on the pyrrole is visible at a chemical shift of 8.9 ppm (s, 8H).

[0038] Figure 2 This is a molecular synthesis route for Por-COF prepared in Example 1. A porphyrin-based covalent organic framework is generated by a Schiff base reaction between amino groups and aldehyde groups.

[0039] Figure 3 and Figure 4 The SEM and TEM images of Por-COF prepared in Example 1 are shown respectively. Figure 3 and Figure 4 It can be seen from the figure that Por-COF is a relatively regular sphere with a size of about 600 nm.

[0040] Figure 5 This is the infrared spectrum of Por-COF prepared in Example 1. Figure 5 It can be seen that TAPP is at 3460cm -1 and 3370cm -1 The amino characteristic peak at 1700 cm -1The aldehyde absorption peaks at 100 nm and 100 nm respectively were detected in the infrared spectrum of the synthesized Por-COF, while these two peaks did not appear in the infrared spectrum of the synthesized Por-COF, indicating that TAPP and OBMF formed an imine bond through the Schiff base condensation reaction and Por-COF was successfully synthesized.

[0041] Figure 6 The XPS spectrum (a) and high-resolution C 1s, N 1s and O 1s XPS spectra (bd) of Por-COF prepared in Example 1 are shown. Figure 6 (a) It can be seen that the measurement spectrum of Por-COF shows the signals of C 1s, N 1s, and O 1s. Figure 6 In (bd), the C1s spectrum of Por-COF contains four distinct peaks. The peak at a binding energy of 286.7 eV is attributed to the carbon-nitrogen double bond in the porphyrin ring, confirming the involvement of TAPP in the reaction. The remaining peaks are CC / C=C, CO / CN, and CH, with binding energies corresponding to 284.5 eV, 285.5 eV, and 288 eV, respectively. The O 1s XPS spectrum is divided into two types of peaks: CO and HO. The peak at a binding energy of 531.7 eV is attributed to the carbon-nitrogen single bond, confirming the involvement of OBMF in the reaction. The N 1s XPS spectrum is divided into two types of peaks: CN and C=N. The peak at a binding energy of 398.3 eV is attributed to the carbon-nitrogen double bond, also known as the iminoamine bond, strongly confirming the synthesis of Por-COF.

[0042] Figure 7 The PXRD spectrum of Por-COF prepared in Example 1 and the simulated PXRD and its difference (a) and the side view of AA stacking unit cell and AA stacking (b). Figure 7 The PXRD data in (a) show that the Por-COF has good crystallinity. XRD characteristic peaks appear at 10.5° and 20°. In addition, the structure refinement simulation was carried out using MS (Materials Studio) modeling software. Figure 7 (b) It can be seen that the PXRD data are in good agreement with the theoretical model of Por-COF with AA stacking sequence. At the same time, the PXRD spectrum is further refined by Rietveld, and the optimized unit cell parameters are α=90°, β=90.3°, Rwp=8.74%, Rp=6.83%.

[0043] Figure 8 The Por-COF prepared in Example 1 was heated by 730 nm laser (20 mW / cm 2 ) Absorption spectrum of DPBF solution after irradiation (a), absorption spectrum of DPBF+Por-COF solution (b), 1 Time-dependent degradation curve of DPBF by O2 (c). Figure 8 As shown in (a), pure DPBF solution was exposed to 730nm laser (20mW / cm 2 ) irradiated, the absorbance was measured every 2 minutes and it was found that the absorbance remained almost constant. On the contrary, the absorption decay rate of DPBF solution containing Por-COF decreased significantly with the extension of irradiation time ( Figure 8 b), the absorption decays to 65% of the initial absorption, indicating that 1 O2 and reacted with DPBF. The absorbance of the Por-COF treatment group decreased significantly in the first 2 minutes. The reason is that the photothermal conversion efficiency of Por-COF is significant, which triggers a rapid increase in temperature and has a synergistic antibacterial effect of PTT and PDT. Figure 8 As can be seen in (c), the absorbance of DBPF decreases rapidly as Por-COF is exposed to laser, which also verifies the significant 1 O2.

[0044] Figure 9 The Por-COF solution prepared in Example 1 at different concentrations and deionized water were detected at 730 nm (2 W / cm 2 ) Temperature rise curve under laser irradiation (a) and Por-COF (150 μg / mL) at 730 nm (2 W / cm 2 ) 5 heating and cooling cycle curves under laser irradiation and infrared thermal imaging of the heating process (bc). Figure 9 (a) It can be seen that with pure deionized water as the control group, the Por-COF dispersion was 2 ) after irradiation for 6 minutes, the temperature change curves of different gradient concentrations (0-150μg / mL). It can be observed that after water as the control group was continuously irradiated for 6 minutes, its temperature remained basically unchanged. On the contrary, the temperature of the Por-COF dispersion solution increased significantly after irradiation for 6 minutes, and the temperature increase depended on the concentration and irradiation time. Among them, the concentration of 150μg / mL was irradiated under laser for 1 minute, and the temperature quickly rose to 46.5℃, indicating that Por-COF has good photothermal conversion ability. After being irradiated for 6 minutes, the temperature of the Por-COF dispersion solution rose from 29.6℃ to 69.5℃. Figure 9 In (b), 5 cycles of continuous heating and cooling were tested, and it was found that the heating and cooling curves had basically no significant fluctuations, indicating that Por-COF has excellent photothermal stability. Figure 9 In (c), the infrared thermal imager was used to record the dispersion of 150 μg / mL Por-COF at 730 nm (2 W / cm 2 ) Heating process after laser irradiation for 6 min.

[0045] Example 2

[0046] Preparation of porphyrin-based covalent organic frameworks:

[0047] 1) Add p-nitrobenzaldehyde (7.6 g) to propionic acid (150 mL) and propionic anhydride (35 mL) at room temperature under N2 protection. Stir magnetically for 30 minutes. Add pyrrole (4.7 mL dissolved in 20 mL propionic anhydride) dropwise to the solution using a separatory funnel. React at 150°C for 3 hours (under N2 protection). Cool to reflux. After cooling to room temperature, filter the precipitate, rinse with methanol, and then dry in an oven at 100°C. Grind the crude product into a solid powder in a mortar and pestle. Pour the powder into a three-necked flask, heat to 70°C, and slowly add pyridine dropwise. Continue magnetic stirring for 30 minutes. Then terminate the reaction, wash with propionic acid, and collect the solid (TNPP).

[0048] 2) 1.8 g TNPP, 75 mL HCl, and 7 g SnCl2 (dissolved in 20 mL HCl) were mixed under N2 flow and magnetically stirred at room temperature for 2 h. The mixture was then heated in an oil bath at 70°C for 0.5 h. After the reaction was complete, the mixture was cooled to room temperature and the pH was adjusted to a weakly alkaline state by adding aqueous ammonia. The product TAPP was extracted with DMF and dichloromethane and further purified by rotary evaporation.

[0049] 3) TAPP (135 mg), 1,3,5-trimethylbenzene (10 mL), and glacial acetic acid (6 mol / L, 2 mL) were placed in a high-temperature reactor. Anhydrous ethanol was added dropwise and magnetically stirred for 10 minutes. OBMF (242 mg) was then added and stirred for 10 minutes. The high-temperature reactor was then placed in an oven at 120°C for 12 hours. A purple precipitate was obtained, which was centrifuged with anhydrous ethanol (5000 rpm) to neutralize the resulting Por-COF powder, which was then dried in an oven.

[0050] Example 3

[0051] Antibacterial ability test of porphyrin-based covalent organic frameworks:

[0052] The ultrasonically dispersed Por-COF dispersion prepared in Example 1 was dispersed in the broth used to culture bacteria at concentrations of 0, 75, and 150 μg mL -1 At 2W·cm -2 The cells were irradiated with a 730nm laser for 6 minutes, incubated at 37°C for 4 hours, diluted 10,000-fold with phosphate buffer, and 100 μL of the diluted suspension was applied to Luria Bertani solid medium. The cells were 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 sterilization rate.

[0053] The sterilization effect of the Por-COF dispersion prepared in Example 1 after stripping was measured by plate counting method. Figure 10 The results showed that the antibacterial properties of Por-COF increased with the increase of concentration, and at a concentration of 150 μg·mL -1 When tested on E. coli and Staphylococcus aureus, the sterilization rate was over 99%. When comparing the results of the two bacteria, it was found that photothermal sterilization was more effective against E. coli than against Staphylococcus aureus. This is due to the difference in cell wall composition between Gram-negative and Gram-positive bacteria.

[0054] Application examples:

[0055] The present invention first prepares a WPUS by a reasonable preparation process 1.5 / Por-COF-X wt% composite film, the composite film has excellent mechanical properties and outstanding light-to-heat conversion efficiency, and has a good bactericidal effect at relatively low concentrations. Bacteria can be inactivated in a short time, and the sterilization rate can reach more than 99%.

[0056] Application Example 1

[0057] Preparation of bio-based waterborne polyurethane (WPU):

[0058] In the first step, 21g of polytrimethylene ether glycol (PO3G), 9g of polypropylene glycol (PPG), and 12.33g of isophorone diisocyanate (IPDI) were added to a 150mL three-necked flask. A small amount of acetone was added to prevent viscosity increase. The reaction was mechanically stirred in a constant temperature oil bath (pre-installed with a condenser reflux device and nitrogen gas for protection). The propeller stirring speed was set at around 450r / min, and the heating reaction temperature was set to 90°C for 2h.

[0059] In the second step, the reaction temperature was changed to 80°C, and 1.4 g of 2,2-dihydroxymethylpropionic acid (DMPA), bis(4-hydroxyphenyl) disulfide (HPS) (dissolved in acetone in advance) and 1.4 g of 1,4-butanediol (BDO) were added to the reaction system in sequence to carry out chain extension reaction for 2 h.

[0060] In the third step, the reaction temperature was set to 65°C and one drop of dibutyltin dilaurate (DBTDL) was added. The reaction was continued for 2 hours. A small amount of acetone was added to reduce the viscosity of the reaction system to prevent gelation. The NCO content was then tested to see if it reached the theoretical value (using di-n-butylamine titration). The reaction temperature was set to 45°C and 1.05g of triethylamine (TEA) was added for neutralization. The neutralization reaction lasted for 0.5 hours.

[0061] The fourth step is to cool to room temperature, take out the three-necked flask and place it in an ice water bath, stir it at high speed with a disperser stirrer and add a certain mass of deionized water for high-speed shear emulsification (theoretical solid content is 30%), and finally add 0.3g of anhydrous ethylenediamine (EDA) (weighed half an hour in advance and added to deionized water in a mass ratio of 1:8) and stir at low speed for 10 minutes, then let it stand for 6 hours, and finally remove the acetone solvent by a rotary evaporator to obtain WPUS. x Dispersion emulsion, where x represents the mass of HPS input. When the mass of HPS input is 0.5g and 1.5g, WPUS is prepared respectively. 0.5 、WPUS 1.5 Dispersion emulsion.

[0062] Application Example 2

[0063] WPUS 1.5 Preparation of Por-COF-X wt% composite films:

[0064] First, prepare a 500 μg / mL Por-COF dispersion in deionized water. 1.5 The emulsion (prepared in Example 1) was added to the test tube, and then the required amount of Por-COF dispersion (prepared in Example 1) was pipetted and mixed with ultrasound for 15 minutes. The mixed emulsion was poured into a polytetrafluoroethylene mold and dried naturally at room temperature for 2 days, and then placed in an oven at 50°C for 6 hours to obtain WPUS. 1.5 / Por-COF-Xwt% composite film. (X-wt% is the mass ratio of Por-COF in the corresponding composite film. WPUS was prepared according to 0, 0.04wt%, and 0.08wt% respectively. 1.5 Film, WPUS 1.5 / Por-COF-0.04wt% composite film, WPUS 1.5 / Por-COF-0.08wt% composite film).

[0065] Application Example 3

[0066] WPUS 1.5 / Antibacterial ability test of Por-COF-Xwt% composite film:

[0067] First, 50 μL of glycerol-preserved Escherichia coli and Staphylococcus aureus were added to 50 mL of Luria-Bertani broth, shaken, and then placed in a 37°C constant temperature shaker for 8.5 h to obtain 1×10 9 CFU / mL (colony forming units) of Staphylococcus aureus and Escherichia coli. Use a pipette to draw 5 μL of Staphylococcus aureus droplets on WPUS1.5 / Por-COF-Xwt% films were irradiated with near-infrared light for 10 minutes or left unexposed. The bacterial suspension was then rinsed from the film with 5 mL of PBS. 100 μL of the culture solution containing the treated bacteria was pipetted into a centrifuge tube and then 2.9 mL of PBS was added and shaken thoroughly. 100 μL of the culture solution from the centrifuge tube was then dropped onto LB agar medium, shaken thoroughly, and incubated in a 37°C incubator for 16 hours. The treated colonies were then counted using the agar plate method to obtain images of the colonies. Bacterial counts were also performed to calculate the sterilization rate.

[0068]

[0069] Figure 11 Bio-based waterborne polyurethane (WPUS) prepared in Application Example 1 and Application Example 2 1.5 ) and WPUS 1.5 Mechanical properties curve of / Por-COF-Xwt% composite film. Figure 11 It can be seen that WPUS 1.5 The tensile strength of the membrane is 3.1 MPa. After adding Por-COF, WPUS 1.5 The mechanical properties of WPUS / Por-COF composite films are significantly improved. When the addition amount of Por-COF is 0.04wt%, 1.5 / Por-COF film has a maximum strength of 8.7MPa, compared with WPUS 1.5 The film strength is significantly improved. Especially when the addition amount reaches 0.08wt%, WPUS 1.5 The Por-COF film achieved a maximum strength of 12 MPa and a strain of 2722%. Por-COF, introduced as a functional filler into the polyurethane system, enhances the crosslinking within the polyurethane through non-covalent or covalent interactions. The organic ligands in Por-COF contain hydrogen bonding groups that interact with the polyurethane molecular chains through hydrogen bonding, further strengthening the polymer's network structure.

[0070] Figure 12 WPUS prepared in Example 2 1.5 / Por-COF-Xwt% composite film in the dark and near infrared 730nm (2W / cm 2 ) Staphylococcus aureus and Escherichia coli were infected with WPUS with different Por-COF contents under laser irradiation. 1.5 Photographs of cultures on agar plates after film treatment (ab) and Staphylococcus aureus and Escherichia coli cultured on WPUS containing different Por-COF contents 1.5The number of colonies cultured on the agar plate after film treatment was used for statistical analysis of bacterial activity (cd) (Mean±SD, n=3). Figure 12 As shown in the figure, the antibacterial properties of the composite film can be improved with the increase of Por-COF content, and when the content is 0.08wt%, the sterilization rate against Escherichia coli and Staphylococcus aureus is more than 99%.

[0071] The above content is merely an example and explanation of the concept of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A porphyrin-based covalent organic framework nanomaterial, the structural formula of which is shown below:

2. A porphyrin-based covalent organic framework nanomaterial, characterized in that: The nanomaterial has a spherical structure with a diameter of 400-600nm and a photothermal conversion efficiency of 77% under 730nm near-infrared light irradiation.

3. A method for preparing the porphyrin-based covalent organic framework nanomaterial according to claim 1, characterized in that: First, p-nitrobenzaldehyde and pyrrole were used as raw materials for a condensation reaction to obtain 5,10,15,20-alkyl(4-nitrophenyl)porphyrin (TNPP); then, under heating conditions, the nitro group of TNPP was redox-treated with anhydrous stannous chloride and dilute hydrochloric acid to obtain 5,10,15,20-tetrakis(4-aminophenyl)porphyrin (TAPP); finally, 5,10,15,20-tetrakis(4-aminophenyl)porphyrin (TAPP) and bis-(5-formylfurfuryl) ether (OBMF) were reacted under high temperature conditions through a Schiff base condensation reaction to obtain porphyrin-based covalent organic framework nanomaterials (Por-COF).

4. The method according to claim 3, wherein The preparation steps are as follows: 1) First, p-nitrobenzaldehyde is used as the raw material, propionic acid and propionic anhydride are added, nitrogen is passed through the mixture at room temperature, magnetic stirring is performed, and pyrrole is added dropwise to react to obtain TNPP; 2) Using TNPP as a raw material, anhydrous stannous chloride and dilute hydrochloric acid are added to carry out a redox reaction. After the reaction is completed, the mixture is cooled to room temperature and ammonia is added to adjust the pH value to a weak alkaline state. The mixture is extracted with DMF and dichloromethane to obtain TAPP; 3) TAPP, OBMF, 1,3,5-trimethylbenzene, and glacial acetic acid were poured into a high-temperature reactor, and anhydrous ethanol was added dropwise with magnetic stirring to produce Por-COF by a Schiff base condensation reaction under a solvothermal method.

5. The method according to claim 4, wherein Step 1) The specific steps for preparing TNPP are as follows: the raw material p-nitrobenzaldehyde (7.6 g) is added to propionic acid (100 mL) and propionic anhydride (35 mL) and N2 protection is passed through at room temperature, and magnetic stirring is performed for 30 minutes. Pyrrole (4.7 mL dissolved in 10 mL propionic anhydride) is added dropwise to the solution using a separatory funnel, and the mixture is reacted at 150°C for 3 hours (N2 protection), cooled and refluxed, and after cooling to room temperature, the precipitate is filtered and rinsed with methanol, and then dried in an oven at 100°C; the crude product is ground into a solid powder in a mortar and poured into a three-necked flask, heated to 70°C, and pyridine is slowly added dropwise. Magnetic stirring is continued for 30 minutes, and then the reaction is terminated, washed with propionic acid, and the solid (TNPP) is collected.

6. The method according to claim 4, wherein Step 2) The specific steps for preparing TAPP are as follows: 1.8 g TNPP, 75 mL HCl, and 7 g SnCl2 (dissolved in 20 mL HCl) are mixed and purged with N2, and magnetically stirred at room temperature for 2 hours. Then, the mixture is heated in an oil bath at 70°C for 0.5 hours. After the reaction is completed, the mixture is cooled to room temperature and ammonia is added to adjust the pH to a weak alkaline state. The mixture is extracted with DMF and dichloromethane, and further purified by rotary evaporation to obtain the TAPP product.

7. The method according to claim 4, wherein Step 3) The specific steps for preparing Por-COF are as follows: first, TAPP (135 mg), 1,3,5-trimethylbenzene (10 mL), and glacial acetic acid (6 mol / L, 2 mL) are poured into a high-temperature reactor container, anhydrous ethanol is added dropwise and magnetically stirred for 10 minutes, and then OBMF (242 mg) is added and stirred for 5 minutes; then the high-temperature reactor is placed in an oven at 120°C for 12 hours; a purple precipitate is obtained, which is centrifuged with anhydrous ethanol (5000 r / min) to neutralize and placed in an oven to dry to obtain the product Por-COF.

8. Use of the porphyrin-based covalent organic framework nanomaterial as claimed in claim 1 as a photothermal / photodynamic synergistic antibacterial material.

9. The use of the porphyrin-based covalent organic framework nanomaterial in polyurethane according to claim 1, characterized in that: It is compounded with polyurethane to prepare a composite film, which is used as a photothermal / photodynamic synergistic antibacterial material.

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