Porphyrin-based covalent organic framework, porphyrin-based covalent organic framework / solanesol composite material and preparation method and application of porphyrin-based covalent organic framework / solanesol composite material
By developing porphyrin-based covalent organic framework/sanilol composites, the problems of easy aggregation and quenching of photosensitizers in the physiological environment are solved, and efficient photothermal and photodynamic bactericidal effects are achieved, and the natural defense mechanism against bacterial infection is enhanced.
Patent Information
- Application Number
- CN202411696053.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-25
- Publication Date
- 2025-02-25
AI Technical Summary
Existing photosensitizers are prone to aggregation and quenching in the physiological environment, and are limited by the penetration depth of light and the oxygen concentration in the microenvironment, resulting in limited treatment efficiency. At the same time, a single chemical bactericidal method may also cause drug resistance problems.
A porphyrin-based covalent organic framework/sanilol composite material was developed, and a porphyrin-based covalent organic framework was prepared by reacting 5,10,15,20-tetra-(4-aminophenyl)porphyrin with 2,5-bis(allyloxy)terephthalaldehyde and composited with solanol to form a composite bactericidal material with high efficiency photothermal and photodynamic effects.
This composite material can effectively prevent the self-aggregation and quenching of photosensitizers, improve the effect of photothermal and photodynamic therapy. At the same time, through the immune activation of solanol, the host's natural defense mechanism is enhanced, the occurrence of drug resistance is reduced, and a stronger bactericidal effect is achieved.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of advanced functional materials and biomedicine, and in particular to a porphyrin-based covalent organic skeleton, a porphyrin-based covalent organic skeleton / solanesol composite material, and a preparation method and application thereof. Background Art
[0002] Bacterial infection has become a serious public health problem worldwide, posing a huge medical burden. According to statistics, bacterial infection was the second leading cause of death in the world in 2019, resulting in 7.7 million deaths. More seriously, more than 50% of deaths were caused by one of the five major pathogens: Staphylococcus aureus, Escherichia coli, Streptococcus pneumoniae, Klebsiella pneumoniae, and Pseudomonas aeruginosa. These pathogens are not only widespread, but also closely related to the problem of antibiotic resistance. At the same time, the phenomenon of antibiotic resistance is spreading around the world, making many common infections difficult to treat, and many bacterial infections that were once curable have become difficult to control or even fatal. Therefore, the development of a new treatment for bacterial infections, especially one that can effectively deal with the problem of drug resistance, has become an urgent need for medical research today. New therapies must not only have strong bactericidal capabilities, but also reduce or avoid the possibility of bacterial resistance.
[0003] Photo-sterilization (including photothermal sterilization and photodynamic sterilization) is a new type of bactericidal therapy that uses photosensitizers to convert light energy into heat energy or reactive oxygen species, thereby causing irreversible damage to bacteria and achieving therapeutic effects. However, most photosensitizers have poor water solubility, are prone to self-aggregation and quenching in physiological environments, and have poor photostability, which seriously weakens their antibacterial effects. In addition, the efficiency of photo-sterilization is also limited by the limited penetration depth of light and insufficient oxygen supply in the microenvironment. Therefore, there is an urgent need to develop a new type of phototherapy agent with enhanced efficacy to achieve efficient treatment of bacterial infections.
[0004] Solanesol is a natural compound extracted from Solanaceae plants. It is widely found in plants such as tobacco, potatoes, and tomatoes. It belongs to the long-chain unsaturated alcohols and has a variety of biological and pharmacological activities. For example, it has strong antioxidant properties, can scavenge free radicals, reduce oxidative stress, prevent cell damage and delay aging. Solanesol can also inhibit the release of inflammatory mediators and regulate inflammatory responses, and is expected to be used in the treatment of inflammatory diseases such as arthritis and enteritis. Its anti-tumor activity has also been confirmed in some studies. It can inhibit the proliferation of cancer cells and induce their apoptosis, and has potential application value in chemotherapy. In addition, Solanesol is a precursor of important compounds such as coenzyme Q10 and vitamin K, promotes the synthesis of these substances, and contributes to physiological processes such as energy metabolism, anti-oxidation and blood coagulation. Solanesol can also enhance the immune system and improve the body's resistance to disease, which may be helpful in the prevention and treatment of chronic diseases such as diabetes and atherosclerosis. In summary, Solanesol exhibits a variety of biological activities in terms of antioxidant, anti-inflammatory, and anti-tumor, and has a wide range of application potential as an adjuvant therapeutic agent. Summary of the invention
[0005] The technical problem to be solved by the present invention is to provide a porphyrin-based covalent organic skeleton, a porphyrin-based covalent organic skeleton / solanesol composite material, and a preparation method and application thereof, which successfully overcomes the problems of traditional photosensitizers being easily aggregated and quenched in a physiological environment and having limited therapeutic efficiency due to the depth of light penetration and the oxygen concentration in the microenvironment; at the same time, it avoids the problem of drug resistance caused by a single chemical sterilization method, and provides a safer and more efficient sterilization strategy and bacterial infection treatment method.
[0006] The technical problem to be solved by the present invention is achieved through the following technical solutions:
[0007] A porphyrin-based covalent organic framework, wherein the porphyrin-based covalent organic framework (TB) is prepared by reacting a 5,10,15,20-tetrakis-(4-aminophenyl)porphyrin (TAPP) monomer with a 2,5-bis(allyloxy)terephthalaldehyde (BATA) monomer, wherein TB has a structure shown in formula I, TAPP has a structure shown in formula II, and BATA has a structure shown in formula III:
[0008]
[0009] Preferably, in the above technical solution, the porphyrin-based covalent organic framework is prepared by the following method: mixing TAPP and BATA, adding a catalyst and an organic solvent, ultrasonically treating, degassing, washing and drying to obtain TB.
[0010] A porphyrin-based covalent organic framework is used in the fields of gas storage, catalysis, sensing and separation.
[0011] A porphyrin-based covalent organic skeleton / solanesol composite bactericidal material, the composite bactericidal material comprises solanesol and a porphyrin-based covalent organic skeleton.
[0012] A method for preparing a porphyrin-based covalent organic framework / solanesol composite bactericidal material comprises the following steps:
[0013] (1) 5,10,15,20-tetrakis-(4-aminophenyl)porphyrin (TAPP) and 2,5-bis(allyloxy)terephthalaldehyde (BATA) are mixed, a catalyst and an organic solvent are added, ultrasonic treatment is performed, degassing is performed, and washing and drying is performed to obtain a product porphyrin-based covalent organic framework (TB);
[0014] (2) Weigh pure solanesol into a volumetric flask, and dilute to volume with ethanol-water to obtain a solanesol solution;
[0015] (3) Weighing a certain amount of porphyrin-based covalent organic framework and solanesol solution, mixing them, placing them on a shaker, shaking, centrifuging and collecting the product, and drying them to obtain a porphyrin-based covalent organic framework / solanesol composite antibacterial material (TB-Sol).
[0016] Preferably, in the above technical solution, in step (1),
[0017] The molar ratio of TAPP to BATA is 1:(2-4), preferably 1:2;
[0018] The catalyst is an acid solution or an alkaline solution, the acid solution is an acetic acid solution, a p-toluenesulfonic acid solution, a p-nitrobenzenesulfonic acid solution or a trifluoroacetic acid solution, the amount of the catalyst is 5%-20% of the volume of the entire reaction system, preferably 10%, and the concentration of the acid solution is 3M;
[0019] The organic solvent is a mixture of one or more of dioxane, mesitylene, n-butanol, tetrahydrofuran, and benzyl alcohol, preferably a mixture of o-dichlorobenzene and n-butanol in a volume ratio of 1:9-7:3, more preferably a 1:1 mixture.
[0020] Preferably, in the above technical solution, in step (1),
[0021] The ultrasonic treatment time is 5-60 min, preferably 10 min;
[0022] The degassing reaction is a three-cycle freeze-fill-nitrogen-vacuum-thaw reaction, the reaction temperature is 20-200°C, and the reaction time is 1-5 days;
[0023] The washing and drying process includes centrifugation at a speed of 5000-10000 rpm; the washing solvent is one or more of tetrahydrofuran, ethanol and acetonitrile; the washing times are 3-6 times, and vacuum drying is performed.
[0024] Preferably, in the above technical solution, in step (2), the volume ratio of ethanol to water in ethanol-water is 9:1, and the concentration of the solanesol solution is 0.2-0.5 mg / mL.
[0025] Preferably, in the above technical solution, in step (3), the feed ratio of the porphyrin-based covalent organic framework to the solanesol solution is 1:2; the oscillation condition is 200 rpm for 1-5 hours; and the centrifugation condition is 10000 rpm for 5 minutes.
[0026] Application of a porphyrin-based covalent organic framework / solanesol composite bactericidal material in photothermal / photodynamic sterilization for non-disease diagnosis and treatment.
[0027] The above technical solution of the present invention has the following beneficial effects:
[0028] (1) The porphyrin-based covalent organic framework (TB) provided by the present invention can limit the distance between photosensitizer monomer molecules due to its special skeleton structure, reduce the self-aggregation quenching of the photosensitizer while ensuring the high-density aggregation of porphyrin molecules, and has good photothermal conversion performance and high efficiency. 1 O2 generation capability, achieving excellent photothermal and photodynamic effects, effectively preventing the self-aggregation quenching of the photosensitizer and thermal damage caused by continuous exposure to external light sources;
[0029] (2) The TB prepared in the present invention has a large surface area that enhances light absorption capacity, and its porous structure also helps to store oxygen and release reactive oxygen, thereby improving the effect of photodynamic therapy;
[0030] (3) The preparation method of the porphyrin-based covalent organic framework material provided by the present invention does not contain metal during the synthesis process, and the reaction to form the imino bond is reversible, which provides the possibility for the subsequent degradation of the material. These characteristics give TB good biosafety;
[0031] (4) The porphyrin-based covalent organic framework / solanesol composite bactericidal material (TB-Sol) of the present invention, the adsorbed solanesol promotes the activation of the host immune system, and solanesol can enhance the natural defense mechanism against bacterial infection; its combined use with TB can not only improve the efficacy of antibacterial drugs, but also reduce the occurrence of drug resistance, thereby achieving a more potent bactericidal effect. BRIEF DESCRIPTION OF THE DRAWINGS
[0032] The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention.
[0033] Figure 1 Schematic diagram of the porphyrin-based covalent organic framework TB and TB-Sol prepared in Example 1;
[0034] Figure 2 The experimental and simulated X-ray powder diffraction patterns of TB prepared in Example 1;
[0035] Figure 3 The infrared spectra of the monomers TAPP, BATA and the prepared TB used in Example 1;
[0036] Figure 4 is the X-ray powder diffraction pattern of TB prepared in Example 2;
[0037] Figure 5 is the X-ray powder diffraction pattern of TB prepared in Example 3;
[0038] Figure 6 is the X-ray powder diffraction pattern of TB prepared in Example 4;
[0039] Figure 7 is the X-ray powder diffraction pattern of TB prepared in Example 5;
[0040] Figure 8 is a graph showing the singlet oxygen generation capability of TB prepared in Example 1;
[0041] Fig. 9 This is the photothermal effect diagram of the TB prepared in Example 1;
[0042] Fig.10 This is a diagram showing the bactericidal effect of TB prepared in Example 1;
[0043] Fig.11 This is the plate sterilization diagram of TB prepared in Example 1;
[0044] Fig.12 is a graph showing the adsorption capacity of TB prepared in Example 1 for solanesol;
[0045] Fig.13 This is a diagram showing the bactericidal effect of TB-Sol prepared in Example 1.
[0046] Fig.14 This is a plate sterilization chart of TB-Sol prepared in Example 1. DETAILED DESCRIPTION
[0047] Various exemplary embodiments of the present invention will now be described in detail with reference to the accompanying drawings. It should be noted that the relative arrangement of components and steps, numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless otherwise specifically stated.
[0048] Unless otherwise specified, the reagents used in this application are all commercially available or obtained through commercial channels, or can be prepared by referring to existing chemical methods.
[0049] 5,10,15,20-Tetrakis-(4-aminophenyl)porphyrin (TAPP): CAS No.: 22112-84-1, purchased from Jilin Zhongkexun Technology Co., Ltd.; 2,5-Bis(allyloxy)terephthalaldehyde (BATA): CAS No.: 2377871-78-6, purchased from Jilin Zhongkexun Technology Co., Ltd.
[0050] Test method:
[0051] Crystal structure: 30 mg of TB was poured into a mortar and ground for 1 min, then transferred to the center of the sample stage, flattened with a cover glass, and placed in an X-ray diffractometer for measurement.
[0052] Example 1
[0053] A method for preparing a porphyrin-based covalent organic framework / solanesol composite bactericidal material (TB-Sol) that integrates photothermal, photodynamic and chemical sterilization functions is to use the photosensitizer 5,10,15,20-tetrakis-(4-aminophenyl)porphyrin (TAPP) as a structural unit and embed it into the covalent organic framework. This design not only ensures the high density of the photosensitizer, but also effectively reduces its quenching phenomenon caused by self-aggregation, thereby improving its photothermal and photodynamic efficiency. The adsorbed solanesol can enhance the natural defense mechanism against bacterial infection by promoting the activation of the host immune system. Its combined use with TB can not only improve the efficacy of antibacterial drugs, but also reduce the occurrence of drug resistance, thereby achieving a more potent bactericidal effect.
[0054] The preparation method specifically comprises the following steps:
[0055] (1) 40.8 mg of 5,10,15,20-tetrakis-(4-aminophenyl)porphyrin (TAPP), 29.5 mg of 2,5-bis(allyloxy)terephthalaldehyde (BATA), 1.5 mL of o-dichlorobenzene and 1.5 mL of n-butanol were placed in a Schlenk reaction tube and ultrasonicated for 5 minutes. Subsequently, 0.3 mL of 3M acetic acid was added and ultrasonic mixing was continued for 5 minutes to obtain a reaction solution.
[0056] (2) the mixture was degassed three times in a Schlenk reaction tube by freeze-fill with nitrogen-vacuum-thaw cycle, sealed, and reacted at 120° C. for 5 days;
[0057] (3) After the reaction solution was cooled to room temperature, it was centrifuged and washed five times with tetrahydrofuran, and vacuum dried at 60°C to collect the final product (TB);
[0058] (4) Weigh 5 mg of pure solanesol into a 10 mL volumetric flask and dilute to volume with ethanol-water (9:1) to obtain a solanesol solution.
[0059] (5) Weigh 1 mg of porphyrin-based covalent organic framework into a 2 mL centrifuge tube, add 1 mL of solanesol solution, place the centrifuge tube on a shaker with a set temperature, shake at 200 rpm for 5 hours, collect the product by centrifugation (10000 rpm, 5 min), and dry to obtain a porphyrin-based covalent organic framework / solanesol composite antibacterial material (TB-Sol).
[0060] The prepared porphyrin-based covalent organic framework (TB) was structurally characterized, and the results are as follows:
[0061] Figure 2 is the X-ray powder diffraction pattern, from Figure 2 It can be seen that the porphyrin-based covalent organic framework material (TB) has an obvious characteristic diffraction peak at 3.5°, and this characteristic diffraction peak is similar to the simulated AA stacking diffraction peak, but is quite different from the simulated AB stacking diffraction peak, indicating that the obtained porphyrin-based covalent organic framework is constructed in an AA stacking mode.
[0062] Figure 3 The infrared spectra of monomers TAPP, BATA and prepared TB are shown in Figure 1. Figure 3 It can be seen that the characteristic peak of the aldehyde group of monomer BATA in TB (1679cm -1 ) and the amino characteristic peak of monomer TAPP (3200-3400cm -1 ) disappeared, and the characteristic peak of imine bond appeared (1615cm -1 ), indicating that TB was successfully synthesized.
[0063] Example 2
[0064] The mixed solvent in Example 1 was adjusted to o-dichlorobenzene / dioxane (DCB / Diox), benzyl alcohol / n-butanol (Ba / BuOH), and benzyl alcohol / dioxane (Ba / Diox), and the mixture was reacted at 120° C. for 3 days; the rest was consistent with Example 1 to obtain a porphyrin-based covalent organic framework material (TB).
[0065] The obtained porphyrin-based covalent organic framework material (TB) was subjected to performance tests, and the test results are as follows:
[0066] Figure 4 is the X-ray powder diffraction pattern, from Figure 4 It can be seen that the TB obtained with o-dichlorobenzene / dioxane (DCB / Diox), benzyl alcohol / n-butanol (Ba / BuOH) and benzyl alcohol / dioxane (Ba / Diox) as reaction systems has a lower characteristic diffraction peak at 3.5°, indicating that TB can be effectively prepared in a variety of solvent systems, and the TB prepared with o-dichlorobenzene / n-butanol as the reaction system has the highest crystallinity.
[0067] Example 3
[0068] The ratio of the o-dichlorobenzene / n-butanol mixed solvent in Example 1 was increased to include 1:9 (v:v), 3:7 (v:v), and 7:3 (v:v), and the rest was kept consistent with Example 1 to obtain a porphyrin-based covalent organic framework material (TB).
[0069] The obtained porphyrin-based covalent organic framework material (TB) was subjected to performance tests, and the test results are as follows:
[0070] Figure 5 is the X-ray powder diffraction pattern, from Figure 5 It can be seen that the characteristic diffraction peak of TB obtained with the reaction systems of 1:9 (v:v), 3:7 (v:v) and 7:3 (v:v) at 3.5° is relatively low, indicating that the o-dichlorobenzene / n-butanol solvent system can effectively produce TB in the volume ratio range of (1:9)-(7:3), and the TB produced by the reaction system of o-dichlorobenzene / n-butanol (1:1, v:v) has the highest crystallinity.
[0071] Example 4
[0072] The reaction temperature in Example 1 was increased to 60° C., 90° C. and 150° C., and the other conditions were kept consistent with Example 1 to obtain a porphyrin-based covalent organic framework material (TB).
[0073] The obtained porphyrin-based covalent organic framework material (TB) was subjected to performance tests, and the test results are as follows:
[0074] Figure 6 is the X-ray powder diffraction pattern, from Figure 6 It can be seen that the characteristic diffraction peak of TB obtained by adjusting the reaction temperature to 60°C, 90°C and 150°C at 3.5° is lower, indicating that TB can be effectively obtained at a reaction temperature of 60-150°C, and the TB obtained at a reaction temperature of 120°C has the highest crystallinity.
[0075] Example 5
[0076] The reaction time in Example 1 was increased to 2, 4, and 5 days, and the other steps were kept the same as in Example 1 to obtain a porphyrin-based covalent organic framework material (TB).
[0077] The obtained porphyrin-based covalent organic framework material (TB) was subjected to performance tests, and the test results are as follows:
[0078] Figure 7 is the X-ray powder diffraction pattern, from Figure 7 It can be seen that the characteristic diffraction peak of TB obtained by adjusting the reaction time to 2, 3, 4, and 5 days at 3.5° is lower, indicating that TB can be effectively obtained when the reaction time is 2-5 days, and the crystallinity of TB obtained when the reaction time is 5 days is the highest.
[0079] Example 6
[0080] The TB prepared in Example 1 was used as a photosensitizer, and its photodynamic properties were investigated.
[0081] Photodynamic performance: 1 The photodynamic properties of TB were studied using the O2 indicator 9,10-anthracenediyl-bis(methylene)dimalonic acid (ABDA).
[0082] The specific operation is as follows: 100 μL ABDA solution and 9.9 mL TB solution were mixed in a 50 mL centrifuge tube. The final concentrations of ABDA and TB were 5×10 -3 mol L -1 , 200 μg mL -1 Then different power densities (50, 100, 150 mW cm -2 ) was irradiated with a white LED light for different time periods, 1 mL of the irradiated solution was taken out and centrifuged, and the ultraviolet absorption spectrum of the supernatant after centrifugation was measured with a UV-visible near-infrared spectrophotometer, and the degradation rate of ABDA was calculated; the calculation formula of the degradation rate is as follows:
[0083] The degradation rate of ABDA = 1-A / A0(1),
[0084] Where A0 and A are the ultraviolet absorption intensity of ABDA solution at 377 nm before and after illumination, respectively.
[0085] Figure 8 is a graph of the ability to produce singlet oxygen; from Figure 8 Figures A and B show that: pure ABDA illumination (100mW cm -2 ) after 30 min, its absorbance did not show a significant decrease. However, the absorbance of ABDA in the TB system decreased significantly over time and showed irradiation power dependence. -2 The degradation rate of ABDA was about 91.2% after 30 minutes of white light irradiation, which indicates that TB has good photodynamic properties.
[0086] Example 7
[0087] The TB prepared in Example 1 was used as a photosensitizer, and its photothermal properties were investigated.
[0088] TB was dispersed in PBS solution to obtain TB solution (200 μg mL -1), then 1 mL of the solution was added to a 48-well cell culture plate and illuminated with white LED light for 30 min (1 mL of PBS was used as a control) at a power density of 100 mW cm -2 , using a FLIR thermal imager to record temperature changes during irradiation.
[0089] like Fig. 9 As shown, at 100 mW cm -2 After irradiation with white light for 30 min, TB had good photothermal performance and showed time dependence. -1 The temperature of the TB solution system increased by 19.7°C, while that of the PBS control group increased by only 5°C.
[0090] Example 8
[0091] The TB prepared in Example 1 was used as a photosensitizer to investigate its photothermal / photodynamic / chemical sterilization capabilities.
[0092] Plate coating experiment: 1 mL of bacterial suspension (bacterial concentration is 1×10 7 CFU mL -1 ) was mixed with 200 μg TB and then cultured on a shaker at 37°C and 200 rpm for 30 minutes. Subsequently, the bacterial suspension containing TB was exposed to white LED light for 30 minutes, the bacterial suspension was extracted, and after gradient dilution, it was evenly spread on the solid culture medium. After culturing in a 37°C constant temperature incubator for 24 hours, the number of colonies was counted; the sterilization rate was calculated as follows (2):
[0093] Sterilization rate = 1-(C1 / C0) × 100% (2),
[0094] Among them, C0 is the number of colonies without any treatment, and C1 is the number of colonies after incubation with TB solution.
[0095] like Fig.10 Figure A and Figure B, Fig.11 As shown in Figures A and B, TB exhibits significant bactericidal effects under white light irradiation. -2 After irradiation with white light for 30 minutes, the sterilization rates of TB against Escherichia coli and Staphylococcus aureus reached 82.26% and 66.14%, respectively.
[0096] Example 9
[0097] The TB prepared in Example 1 was used as an adsorbent to investigate its ability to adsorb solanesol.
[0098] Adsorption experiment: Weigh 5 mg of pure solanesol, place it in a 10 mL volumetric flask, dilute with ethanol-water (9:1) to obtain a solanesol solution, take 1 mL of the solanesol solution and wait for HPLC loading. Weigh 1 mg of porphyrin-based covalent organic framework in a 2 mL centrifuge tube, add 1 mL of the solanesol solution, place the centrifuge tube on a shaker with a set temperature, shake at 200 rpm for 5 hours, centrifuge (10000 rpm, 5 min), take 1 mL of the supernatant and measure HPLC.
[0099] like Fig.12 As shown in Figures A and B of the HPLC results, it can be seen that compared with the solanesol solution, the solanesol content in the supernatant decreased significantly after TB adsorption, indicating that TB has a good adsorption capacity for solanesol. The adsorption capacity of TB is calculated to be 166 mg g -1 .
[0100] Example 10
[0101] Using TB-Sol prepared in Example 1 as a photosensitizer, its photothermal / photodynamic / chemical sterilization capabilities were investigated.
[0102] 1 mL of bacterial suspension (the concentration of bacteria is 1×10 7 CFU mL -1 ) was mixed with 233 μg TB-Sol and then cultured on a shaker at 37°C and 200 rpm for 30 minutes. Subsequently, the bacterial suspension containing TB-Sol was exposed to white LED light for 30 minutes, the bacterial suspension was extracted, and after gradient dilution, it was evenly spread on the solid culture medium. After culturing in a 37°C constant temperature incubator for 24 hours, the number of colonies was counted; the sterilization rate was calculated as follows (2):
[0103] Sterilization rate = 1-(C1 / C0) × 100% (2),
[0104] Among them, C0 is the number of colonies without any treatment, and C1 is the number of colonies after mixing and incubating with TB-Sol solution.
[0105] like Fig.13 Figure A and Figure B, Fig.14 As shown in Figures A and B of the present study, TB-Sol exhibited significant bactericidal effects under white light irradiation, showing an irradiation time dependence. -2 After irradiation with white light for 30 minutes, the sterilization rates of TB-Sol against Escherichia coli and Staphylococcus aureus reached 99.46% and 97.34%, respectively.
[0106] Although the present invention has been disclosed as above by the embodiments, it is not intended to limit the present invention. Any person skilled in the art may make various choices and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention is limited by the claims and their equivalents.
Claims
1. A porphyrin-based covalent organic framework, characterized in that: The porphyrin-based covalent organic framework (TB) is prepared by reacting 5,10,15,20-tetrakis-(4-aminophenyl)porphyrin (TAPP) monomers with 2,5-bis(allyloxy)terephthalaldehyde (BATA) monomers, TB has a structure shown in Formula I, TAPP has a structure shown in Formula II, and BATA has a structure shown in Formula III:
2. The porphyrin-based covalent organic framework according to claim 1, characterized in that The porphyrin-based covalent organic framework is prepared by the following method: TAPP and BATA are mixed, a catalyst and an organic solvent are added, ultrasonic treatment is performed, degassing is performed, and washing and drying are performed to obtain TB.
3. Application of the porphyrin-based covalent organic framework according to any one of claims 1-2 in the fields of gas storage, catalysis, sensing and separation.
4. A porphyrin-based covalent organic framework / solanesol composite bactericidal material, characterized in that: The composite bactericidal material comprises solanesol and the porphyrin-based covalent organic framework according to any one of claims 1-2.
5. A method for preparing a porphyrin-based covalent organic framework / solanesol composite bactericidal material, characterized in that: The following steps are involved: (1) 5,10,15,20-tetrakis-(4-aminophenyl)porphyrin (TAPP) and 2,5-bis(allyloxy)terephthalaldehyde (BATA) are mixed, a catalyst and an organic solvent are added, ultrasonic treatment is performed, degassing is performed, and washing and drying is performed to obtain a product porphyrin-based covalent organic framework (TB); (2) Weigh pure solanesol into a volumetric flask, and dilute to volume with ethanol-water to obtain a solanesol solution; (3) Weighing a certain amount of porphyrin-based covalent organic framework and solanesol solution, mixing them, placing them on a shaker, shaking, centrifuging and collecting the product, and drying them to obtain a porphyrin-based covalent organic framework / solanesol composite antibacterial material (TB-Sol).
6. The method for preparing the porphyrin-based covalent organic framework / solanesol composite bactericidal material according to claim 5, characterized in that: In step (1), The molar ratio of TAPP to BATA is 1:(2-4), preferably 1:2; The catalyst is an acid solution or an alkaline solution, the acid solution is an acetic acid solution, a p-toluenesulfonic acid solution, a p-nitrobenzenesulfonic acid solution or a trifluoroacetic acid solution, the amount of the catalyst is 5%-20% of the volume of the entire reaction system, preferably 10%, and the concentration of the acid solution is 3M; The organic solvent is a mixture of one or more of dioxane, mesitylene, n-butanol, tetrahydrofuran, and benzyl alcohol, preferably a mixture of o-dichlorobenzene and n-butanol in a volume ratio of 1:9-7:3, more preferably a 1:1 mixture.
7. The method for preparing the porphyrin-based covalent organic framework / solanesol composite bactericidal material according to claim 5, characterized in that: In step (1), The ultrasonic treatment time is 5-60 min, preferably 10 min; The degassing reaction is a three-cycle freeze-fill-nitrogen-vacuum-thaw reaction, the reaction temperature is 20-200°C, and the reaction time is 1-5 days; The washing and drying process includes centrifugation at a speed of 5000-10000 rpm; the washing solvent is one or more of tetrahydrofuran, ethanol and acetonitrile; the washing times are 3-6 times, and vacuum drying is performed.
8. The method for preparing the porphyrin-based covalent organic framework / solanesol composite bactericidal material according to claim 5, characterized in that: In step (2), the volume ratio of ethanol to water in the ethanol-water is 9:1, and the concentration of the solanesol solution is 0.2-0.5 mg / mL.
9. The method for preparing the porphyrin-based covalent organic framework / solanesol composite bactericidal material according to claim 5, characterized in that: In step (3), the feed ratio of the porphyrin-based covalent organic framework to the solanesol solution is 1:2; the oscillation condition is 200 rpm for 1-5 hours; and the centrifugation condition is 10000 rpm for 5 minutes.
10. Use of the porphyrin-based covalent organic framework / solanesol composite bactericidal material prepared by the preparation method according to any one of claims 4 to 8 in photothermal / photodynamic sterilization for non-disease diagnosis and treatment.