Copper phthalocyanine covalent organic frameworks, composite films, and methods of making and using the same

Abstract

The present application relates to a kind of copper phthalocyanine covalent organic framework material with photodynamic / chemical dynamic sterilization and its preparation method and application, belong to advanced functional materials and biomedicine technical field.4,4',4",4" '-tetra-(4-amino) phthalocyanine copper (CuTAPc) is used as main structural unit to synthesize covalent organic framework, can limit the distance between photosensitizer, thereby reducing the self-aggregation quenching of photosensitizer, realize good photodynamic effect.Copper ion consumes glutathione overexpressed in bacterial microenvironment at the same time, avoid its consumption to active oxygen, and further trigger fenton-like reaction, produce active oxygen with toxicity, realize chemical dynamic synergistic therapy, effectively avoid the defect that light penetrates limited depth of tissue, have good treatment effect to deep tissue.And based on the material, composite antibacterial membrane is further constructed.The multifunctional material has good stability and active oxygen production capacity, and has good biological safety, has great potential in the field of bacterial infection treatment and fruit and vegetable preservation.

Description

Technical Field

[0001] This invention relates to a copper phthalocyanine covalent organic framework material with photodynamic / chemodynamic synergistic bactericidal ability, its preparation method and application, belonging to the fields of advanced functional materials and biomedical technology. Background Technology

[0002] Bacteria are a vast and widely distributed group of organisms in nature, closely related to human life and work. However, bacterial contamination is a prominent problem in many areas, including health and food safety. For example, chronic wound infections involve bacteria accumulating at the wound site and secreting toxins, significantly increasing inflammatory responses and other complications. Treating bacterial-infected chronic wounds is difficult, time-consuming, and expensive, placing a huge economic burden on patients and society. Foodborne illnesses are also a significant concern, ranking among the highest in incidence rates of all diseases and representing a prominent global health problem. While antibiotics have played a role in treating bacterial infections, their widespread use has led to antibiotic resistance in bacteria, making treatment more difficult. Therefore, there is an urgent need to develop a non-resistant and highly effective antibacterial strategy.

[0003] Photodynamic therapy (PDT) is a therapy that utilizes photosensitizers to generate highly reactive singlet oxygen under irradiation at specific wavelengths. 1 Photosensitive agents (PDT) are a novel antibacterial technology that uses oxygen (H2O2) to kill bacteria. They offer advantages such as high bactericidal efficiency, no drug resistance, harmlessness, eco-friendliness, and low cost. However, most photosensitizers, such as porphyrins, phthalocyanines, and phenothiazines, suffer from poor water solubility, easy self-aggregation and quenching, and their therapeutic efficiency is limited by light penetration depth and oxygen concentration, resulting in poor bactericidal effects. Chemodynamic therapy (CDT), on the other hand, utilizes the bacterial microenvironment to activate drugs, causing a Fenton-like reaction that generates highly oxidizing hydroxyl radicals (·OH) to kill bacteria. CDT relies on the interaction between endogenous H2O2 and a catalyst to undergo a Fenton or Fenton-like reaction. Compared to photosensitive agents (PDT), CDT requires neither oxygen nor an external light source, making it a promising technology for treating bacterial infections.

[0004] Therefore, it is of great significance to prepare a photosensitive bactericidal material that is not prone to self-aggregation and quenching, is not limited by external light sources and oxygen, and can achieve efficient photosensitive bactericidal materials and bactericidal methods based on this. Summary of the Invention

[0005] Technical challenges: Traditional photosensitizers are prone to self-aggregation and quenching, and their treatment efficiency is limited by the depth of light penetration and oxygen concentration, resulting in poor bactericidal effects. Although chemodynamic therapy relies on endogenous H2O2 to generate strong oxidizing hydroxyl radicals (·OH) to kill bacteria, the appropriate introduction of catalysts remains a challenge.

[0006] Technical Solution: To address the above problems, the present invention aims to provide a novel photodynamic / chemidynamic bactericidal material synthesized using a Schiff base reaction solvothermal method, integrating photodynamic and chemidynamic bactericidal properties. Copper phthalocyanine is used as the structural unit to synthesize a covalent organic framework, overcoming the problem of traditional photosensitizers easily aggregating and quenching under physiological conditions. Simultaneously, the appropriate introduction of copper ions triggers a Fenton-like reaction, endowing it with chemidynamic therapeutic effects, solving the problem of therapeutic efficacy being limited by external light sources and oxygen, and achieving a synergistic and highly efficient photodynamic / chemidynamic bactericidal effect.

[0007] The first objective of this invention is to provide a copper phthalocyanine covalent organic framework material with photodynamic / chemodynamic synergistic bactericidal ability: having the structural unit shown in Formula III;

[0008]

[0009] R is selected from C1-C4 alkoxy, ethyleneoxy, propenoxy, acetyleneoxy, and propyneoxy.

[0010] In one embodiment of the present invention, R specifically refers to propyneoxy group.

[0011] Furthermore, the copper phthalocyanine covalent organic framework material is prepared by reacting the amino-copper phthalocyanine compound shown in Formula I with the p-dimethylaldehyde compound shown in Formula II;

[0012]

[0013] A second objective of this invention is to provide a method for preparing the copper phthalocyanine covalent organic framework material, comprising the following steps:

[0014] S1. After mixing the aminocopper phthalocyanine compound shown in Formula I, the p-dimethylaldehyde compound shown in Formula II, and the solvent evenly, continue to add the catalyst and mix evenly to obtain a reaction solution;

[0015] S2. React the reaction solution obtained in step S1 at 20-200℃ for 1-7 days; after the reaction is completed, centrifuge, wash and dry to obtain the copper phthalocyanine covalent organic framework.

[0016] Further, in step S1, the molar ratio of the aminocopper phthalocyanine compound to the p-dimethylaldehyde compound is 1:(2-6).

[0017] Further, in step S1, the solvent is selected from one or a combination of benzyl alcohol, dimethyl sulfoxide, dioxane, mesitylene, n-butanol, and o-dichlorobenzene;

[0018] Preferably, the solvent is a benzyl alcohol / dimethyl sulfoxide solvent system with a volume ratio of 0:10-9:1;

[0019] In some preferred embodiments, in step S1, the solvent is a mixture of benzyl alcohol and dimethyl sulfoxide in a volume ratio of 7:3.

[0020] Furthermore, the catalyst is an acid solution or an alkaline solution.

[0021] Furthermore, the acid includes one of acetic acid solution, p-toluenesulfonic acid solution, p-nitrobenzenesulfonic acid solution, and trifluoroacetic acid solution; the base includes one of sodium hydroxide solution and tetrahydropyrrole solution.

[0022] In some embodiments, in step S2, the reaction solution needs to undergo a freezing-nitrogen purging-vacuuming-thawing cycle before the reaction;

[0023] In some preferred embodiments, the reaction solution described in step S2 needs to undergo three cycles of freezing-nitrogen purging-vacuuming-thawing before the reaction.

[0024] Further, in step S2, the washing solvent is one or more of tetrahydrofuran, ethanol, acetonitrile, and N,N-dimethylformamide.

[0025] In some implementations, in step S2, the number of washing cycles is 3-6; the centrifugation speed is 8000-12000 rpm.

[0026] In one embodiment of the present invention, the aminocopper phthalocyanine compound in step S1 is 4,4',4”,4”'-tetra-(4-amino)phthalocyanine copper (CuTAPc) and the p-dicarboxaldehyde compound is 2,5-bis(prop-2-yn-1-yloxy)-terephthalaldehyde (BPTA), and the condensation reaction is used to prepare the copper phthalocyanine covalent organic framework (CuTAPc-BPTA).

[0027] In one embodiment of the present invention, the ratio of the solvent and the aminocopper phthalocyanine compound in step S1 is 2 mL: 13.99 mg.

[0028] In one embodiment of the present invention, the catalyst in step S1 is acetic acid.

[0029] In one embodiment of the present invention, the volume ratio of the catalyst in the solvent in step S1 is 1%-20%.

[0030] In one embodiment of the present invention, the mixing in step S1 is ultrasonic mixing, and the ultrasonic time is 5-60 minutes.

[0031] In one embodiment of the present invention, the reaction solution described in step S2 needs to undergo three cycles of freezing-nitrogen purging-vacuuming-thawing before the reaction.

[0032] In one embodiment of the present invention, the washing solvent in step S2 is one or more of tetrahydrofuran, ethanol, acetonitrile, and N,N-dimethylformamide; the number of washing cycles is 3-6; and the centrifugation speed is 8000-12000 rpm.

[0033] In one embodiment of the present invention, the drying step S2 is performed using vacuum drying.

[0034] In some embodiments, the copper phthalocyanine covalent organic framework material is prepared into a composite antibacterial membrane, and the preparation method further includes steps S3 and S4 in addition to steps S1 and S2:

[0035] S3. Disperse the copper phthalocyanine covalent organic framework obtained in step S2 in an aqueous solution to obtain a homogeneous solution A; mix chitosan with acetic acid solution and stir at 25-60℃ to obtain a transparent solution B;

[0036] S4. Mix solution A and solution B obtained in step S3, add glycerol, stir until uniform, remove air bubbles in the solution to obtain casting solution, and then cast the casting solution into a film to obtain copper phthalocyanine covalent organic framework composite antibacterial film.

[0037] In some embodiments, in step S3, the copper phthalocyanine covalent organic framework obtained in step S2 is ultrasonically dispersed in an aqueous solution to obtain a homogeneous solution A; chitosan is mixed with an acetic acid solution and stirred at 25-60°C for 2 hours to obtain a transparent solution B.

[0038] In some embodiments, in step S4, solution A and solution B obtained in step S3 are mixed at a volume ratio of 1:2, glycerol is added, and the mixture is stirred until it is completely homogeneous. The mixture is then sonicated for 30 minutes to remove air bubbles from the solution, and a casting solution is obtained. The casting solution is then cast into a film to obtain a copper phthalocyanine covalent organic framework composite antibacterial film.

[0039] Further, in step S3, the mass concentration of the copper phthalocyanine covalent organic framework (CuTAPc-BPTA) is 0.3-1.8 mg / mL;

[0040] Further, in step S3, the mass concentration of chitosan is 10-25 mg / mL; and the volume fraction of the acetic acid solution in step S3 is 1%.

[0041] Furthermore, in step S3, the volume ratio of solution A to solution B is 1:2.

[0042] In some embodiments, in step S4, the mass of glycerol is 80% of the mass of the corresponding chitosan; the casting process specifically involves: slowly pouring the casting solution into a 9×9cm petri dish and drying it at 60°C for more than 18 hours until completely dry.

[0043] A third objective of this invention is to provide applications of the aforementioned copper phthalocyanine covalent organic framework material, which has wide applications in many fields such as life and health and food safety, including but not limited to, applications in the preparation of photodynamic / chemidynamic sterilization products; and / or applications in fruit and vegetable preservation materials; and / or applications in the fields of gas storage, catalysis, sensing, and separation.

[0044] This invention provides a photodynamic / chemidynamic sterilization method for non-disease diagnosis and treatment, wherein the copper phthalocyanine covalent organic framework composite antibacterial membrane described in this invention is used as the sterilization material.

[0045] In one embodiment of the present invention, the photodynamic / chemodynamic sterilization method for non-disease diagnosis and treatment is to coat a copper phthalocyanine covalent organic framework composite antibacterial film and then apply light.

[0046] In one embodiment of the present invention, the copper phthalocyanine covalent organic framework composite antibacterial film prepared by the present invention is used for grape preservation. Specifically, the steps include: wrapping fresh grapes with the copper phthalocyanine covalent organic framework composite antibacterial film, then irradiating them under a suitable light source; after treatment, the grape samples are incubated at a constant temperature, and the samples are photographed and recorded daily.

[0047] Furthermore, the light source is a 650nm laser lamp, and the irradiation time is 30 minutes.

[0048] The beneficial effects of this invention are:

[0049] The copper phthalocyanine covalent organic framework (CuTAPc-BPTA) prepared in this invention, possessing synergistic photodynamic and chemidynamic bactericidal capabilities, exhibits an ordered framework structure that restricts the distance between phthalocyanine molecules, reducing self-aggregation and quenching. Its porous structure facilitates oxygen storage and release of reactive oxygen species. Abundant active sites prevent copper ion leakage and avoid problems such as copper ion poisoning from excessive intake. It can utilize endogenous H₂O₂ to generate reactive oxygen species, addressing the limitation of therapeutic efficacy to external light sources and oxygen, achieving a synergistic and highly efficient bactericidal effect. The reversible reaction in the organic framework to form imine bonds provides the possibility for subsequent degradation of the material, endowing the copper phthalocyanine covalent organic framework (CuTAPc-BPTA) with good biosafety. This photodynamic / chemidynamic bactericidal integrated material possesses good stability and the ability to generate reactive oxygen species, along with excellent biosafety, showing great potential in the treatment of bacterial infections and the preservation of fruits and vegetables. Attached Figure Description

[0050] Figure 1 Schematic diagram of CuTAPc-BPTA, which integrates photodynamic / chemodynamic sterilization, prepared in Example 1;

[0051] Figure 2 Experimental and simulated X-ray powder diffraction patterns of CuTAPc-BPTA prepared in Example 1;

[0052] Figure 3 Infrared spectra of the monomers CuTAPc and BPTA used in Example 1, and the prepared CuTAPc-BPTA.

[0053] Figure 4 Transmission electron microscopy image of CuTAPc-BPTA prepared in Example 1;

[0054] Figure 5 X-ray powder diffraction pattern of CuTAPc-BPTA prepared in Example 2;

[0055] Figure 6 X-ray powder diffraction pattern of CuTAPc-BPTA prepared in Example 3;

[0056] Figure 7 X-ray powder diffraction pattern of CuTAPc-BPTA prepared in Example 4;

[0057] Figure 8 X-ray powder diffraction pattern of CuTAPc-BPTA prepared in Example 5;

[0058] Figure 9 : A graph showing the ability of CuTAPc-BPTA prepared in Example 1 to generate singlet oxygen;

[0059] Figure 10 : Graph showing the ability of CuTAPc-BPTA prepared in Example 1 to consume glutathione;

[0060] Figure 11 : A graph showing the ability of CuTAPc-BPTA prepared in Example 1 to generate hydroxyl radicals;

[0061] Figure 12 Plate sterilization diagram of CuTAPc-BPTA prepared in Example 1;

[0062] Figure 13 Figure 6 shows the grape preservation effect of the copper phthalocyanine covalent organic framework composite antibacterial film CuTAPc-BPTA-CS prepared in Example 6. Detailed Implementation

[0063] To further enhance understanding of the preparation process and technical characteristics involved in this invention, the invention will be further described below with reference to embodiments. Preferred embodiments of the invention will be described below; it should be understood that these embodiments are for better explanation of the invention and are not intended to limit the invention.

[0064] Test method:

[0065] 1. Crystal structure: 30 mg of CuTAPc-BPTA was poured into a mortar and ground for 1 min. Then it was transferred to the center of the sample stage, flattened with a coverslip, and placed in an X-ray diffractometer for determination.

[0066] 2. Photodynamic performance: using 1 The photodynamic properties of CuTAPc-BPTA were studied using 1,3-diphenylisobenzofuran (DPBF) as an O2 indicator. The specific procedure was as follows: 4 mL of DPBF solution (1×10⁻⁶) was added to the solution. -4 mol L -1 Mix thoroughly with 4 mL of CuTAPc-BPTA solution of different concentrations, and dispense the mixture into 2 mL brown centrifuge tubes, 1 mL per tube. The resulting solutions have a concentration of 0 μg / mL. -1 100μg mL -1 200μg mL -1 400μg mL -1 and 600 μg mL -1 Then, using a power density of 100 mW / cm² -2 After irradiating the above solution with a 650nm laser for different times, 1mL of the irradiated solution was taken out, centrifuged, and the ultraviolet absorption spectrum of the supernatant after centrifugation was measured using an ultraviolet-visible-near-infrared spectrophotometer. The degradation rate of DPBF was then calculated. The formula for calculating the degradation rate is as shown in equation (1):

[0067] DPBF degradation rate = 1 - A / A0 (1)

[0068] Where A0 and A are the UV absorption intensities of the DPBF solution at 410 nm before and after illumination, respectively.

[0069] 3. Glutathione Consumption: GSH consumption was analyzed using a DTNB probe. GSH solution was reacted with CuTAPc-BPTA solutions of different concentrations in the dark, with the final GSH concentration being 500 μg / mL. -1 The final concentrations of CuTAPc-BPTA were 0 mg / mL. -1 0.5 mg mL -1 1 mg mL -1 2mg mL -1 3mg mL -1 4mg mL -1 and 5mg mL -1 Centrifuge 1 mL of solution at different time points, and take 100 μL of the supernatant and mix it with 10 μL of DTNB (800 μg / mL). -1Incubate for 10 min. Record the absorbance value of the solution at 412 nm to calculate the GSH consumption rate. The formula for calculating the GSH consumption rate is as shown in equation (2):

[0070] GSH consumption rate = 1 - A / A0 (2)

[0071] Where A0 and A are the UV absorption intensities of the DTNB solution at 412 nm before the reaction and at 412 nm after the reaction, respectively.

[0072] 4. Chemical Kinetic Properties: The chemical kinetic properties of CuTAPc-BPTA were studied using methylene blue (MB) as an OH indicator. Specifically, CuTAPc-BPTA was reacted with glutathione (GSH) in the dark for 12 hours, with the final concentrations of CuTAPc-BPTA and GSH being 5 mg / mL. -1 500μg mL -1 The MB solution, H2O2 solution, and NaHCO3 solution were mixed with the above solution, wherein the final concentrations of MB, H2O2, and NaHCO3 were 10 μg / mL, 10 mM, and 25 mM, respectively, and the final concentrations of CuTAPc-BPTA were 0 μg / mL. -1 100μg mL -1 200μg mL -1 400μg mL -1 and 600 μg mL -1 Then, after reacting the mixture on a shaker in the dark for different times, 1 mL of solution was taken out, centrifuged, and the ultraviolet absorption spectrum of the supernatant after centrifugation was measured using an ultraviolet-visible-near-infrared spectrophotometer. The degradation rate of MB was calculated; the formula for calculating the degradation rate is as shown in equation (3):

[0073] MB degradation rate = 1 - A / A0 (3)

[0074] Where A0 and A are the UV absorption intensities of the MB solution at 663 nm before and after illumination, respectively.

[0075] 5. Plate coating experiment: Bacterial suspension and CuTAPc-BPTA were mixed, with the final concentrations of the bacterial suspension and CuTAPc-BPTA being 1×10⁻⁶. 7 CFU mL -1 400μg mL -1Then, H2O2 was added or not added (final concentration 50 μM), and cultured on a shaking table at 37℃ and 200 rpm for 30 minutes. Subsequently, the bacterial suspension containing CuTAPc-BPTA was exposed to a 650 nm laser lamp for 30 minutes, and the bacterial suspension containing CuTAPc-BPTA and H2O2 was exposed to a 650 nm laser lamp for 10 minutes. The bacterial suspension was extracted, serially diluted, and evenly spread on a solid culture medium. After culturing in a constant temperature incubator at 37℃ for 20-24 hours, the number of colonies was counted; the formula for calculating the sterilization rate is as follows (4):

[0076] Sterilization rate = [1 - (C1 / C0)] × 100% (4)

[0077] Where C0 is the number of colonies without any treatment, and C1 is the number of colonies after incubation with CuTAPc-BPTA solution.

[0078] Example 1: Preparation of CuTAPc-BPTA material:

[0079] Specifically, the steps include the following:

[0080] (1) 13.99 mg of 4,4',4”,4”'-tetra-(4-amino)phthalocyanine copper (CuTAPc, 0.022 mmol) and 10.66 mg of 2,5-bis(prop-2-yn-1-yloxy)terephthalaldehyde (BPTA, 0.044 mmol) were added to a solvent consisting of benzyl alcohol / dimethyl sulfoxide (7:3, v:v, 2.0 mL), and sonicated for 5 minutes. Then, 0.05 mL of acetic acid was added, and sonication was performed for another 5 minutes.

[0081] (2) The mixture was degassed three times in a Pyrex tube using a refrigeration pump-thaw cycle, and then sealed. The resulting mixture was then reacted at 90°C for 4 days.

[0082] (3) After cooling to room temperature, the final product (CuTAPc-BPTA) was collected by centrifugation, washed five times with THF, and dried under vacuum at 60°C.

[0083] Structural and morphological characterization of CuTAPc-BPTA prepared in Example 1:

[0084] Figure 2 The X-ray powder diffraction pattern is shown below. Figure 2 It can be seen that the copper phthalocyanine covalent organic framework material (CuTAPc-BPTA) has a distinct characteristic diffraction peak at 4.58°, which is similar to the simulated AB stacking diffraction peak, but differs significantly from the simulated AA stacking diffraction peak. This indicates that the obtained copper phthalocyanine covalent organic framework is constructed using the AB stacking mode.

[0085] Figure 3 Fourier transform infrared spectra of monomers CuTAPc, BPTA, and the prepared CuTAPc-BPTA; from Figure 3 It can be seen that the characteristic absorption peak of the amino group of monomer CuTAPc in CuTAPc-BPTA (3200-3400 cm⁻¹) -1 ) and the characteristic peak of the aldehyde group of monomer BPTA (1676 cm⁻¹) -1 All of these disappeared, while a characteristic peak of imine bonds (1603 cm⁻¹) appeared in CuTAPc-BPTA. -1 It also retains the characteristic peak of the triple bond (2128 cm⁻¹). -1 This confirms the successful synthesis of CuTAPc-BPTA.

[0086] Figure 4 Transmission electron microscopy image; from Figure 4 It can be seen that CuTAPc-BPTA has a sheet-like structure.

[0087] Performance determination of CuTAPc-BPTA prepared in Example 1:

[0088] Figure 9 A diagram illustrating the ability to produce singlet oxygen; DPBF can be used with... 1 The reaction of O2 to form oxides causes a decrease in the specific absorption wavelength of DPBF at 410. Figure 9 It can be seen that after 30 minutes of illumination, the absorbance of DPBF did not decrease significantly, indicating that DPBF itself has good stability. (The last sentence appears to be incomplete and possibly refers to a different topic: "containing 100 μg mL...") -1 200μg mL -1 400μg mL -1 and 600 μg mL -1 The degradation rates of DPBF in CuTAPc-BPTA solutions of different concentrations were 26%, 41%, 46%, and 60%, respectively. This indicates that CuTAPc-BPTA possesses significant photodynamic properties and produces... 1 The ability of O2 to react is time- and concentration-dependent.

[0089] Figure 10 This graph shows the ability to consume glutathione; GSH consumption was analyzed using a DTNB probe. DTNB is a commonly used chromogenic agent for GSH; a colorless GSH solution reacts with DTNB to produce a pale yellow product with a characteristic absorption peak at 412 nm, which can be used for GSH quantification. Figure 10It can be seen that after 12 hours of reaction, the absorbance of the solution decreased significantly with increasing CuTAPc-BPTA concentration; however, the absorbance of the solution containing only GSH did not decrease significantly over time. After 12 hours, the absorbance of the solution containing 0.5 mg / mL... -1 1 mg mL -1 2mg mL -1 3mg mL -1 4mg mL -1 and 5mg mL -1 The GSH consumption rates in CuTAPc-BPTA solutions of different concentrations were 6.4%, 13%, 36%, 70%, and 96%, respectively. This indicates that CuTAPc-BPTA possesses good glutathione scavenging ability, exhibiting a time- and concentration-dependent effect.

[0090] Figure 11 A graph showing the ability to generate hydroxyl radicals was used; MB was used as a detection reagent to explore the CDT characteristics of CuTAPc-BPTA. MB is easily degraded by ·OH; therefore, the decrease in absorbance of MB at 664 nm to generate ·OH was used as the criterion. From... Figure 11 It can be seen that CuTAPc-BPTA possesses good chemokinetic properties, and the formation of ·OH is time- and concentration-dependent. (Containing 100 μg / mL) -1 200μg mL -1 400μg mL -1 and 600 μg mL -1 After treatment for 60 min, the absorbance of MB in different concentrations of CuTAPc-BPTA solution systems was significantly reduced compared with that of pure MB and MB-H2O2, and the degradation rates of MB were 34%, 67%, 80%, and 92%, respectively.

[0091] Figure 12 For plate sterilization graphs; from Figure 12 It can be seen that CuTAPc-BPTA itself possesses certain chemodynamic bactericidal properties. Under different treatment conditions, the reactive oxygen species it generates exhibits good bactericidal ability. Under dark conditions, CuTAPc-BPTA achieves a 46% bactericidal rate against Escherichia coli and a 66% bactericidal rate against Staphylococcus aureus. After 10 minutes of light exposure, the bactericidal rates against E. coli and Staphylococcus aureus increase to 93% and 89%, respectively. Similarly, it also exhibits certain photodynamic bactericidal properties. Under different treatment conditions, the reactive oxygen species it generates exhibits good bactericidal ability. Under dark conditions, CuTAPc-BPTA achieves a 7% bactericidal rate against E. coli and a 29% bactericidal rate against Staphylococcus aureus. After 30 minutes of light exposure, the bactericidal rates against E. coli and Staphylococcus aureus increase to 80% and 93%, respectively.

[0092] Example 2 Selection of Solvent Components

[0093] In Example 1, the benzyl alcohol / dimethyl sulfoxide mixed solvent was adjusted to benzyl alcohol / dimethyl sulfoxide (1:1, v:v), dioxane / dimethyl sulfoxide (1:1, v:v), mesitylene / dimethyl sulfoxide (1:1, v:v), o-dichlorobenzene / benzyl alcohol (1:1, v:v), or n-butanol / dimethyl sulfoxide (1:1, v:v), and the mixture was reacted at 120°C for 3 days; all other aspects remained the same as in Example 1, and the copper phthalocyanine covalent organic framework material (CuTAPc-BPTA) was obtained.

[0094] The obtained copper phthalocyanine covalent organic framework material (CuTAPc-BPTA) was subjected to performance testing, and the test results are as follows:

[0095] like Figure 5 As shown in the X-ray powder diffraction pattern, CuTAPc-BPTA obtained with dioxane / dimethyl sulfoxide, mesitylene / dimethyl sulfoxide, o-dichlorobenzene / benzyl alcohol, or n-butanol / dimethyl sulfoxide as the reaction system has a low characteristic diffraction peak at 4.58°, indicating that CuTAPc-BPTA can be effectively prepared in various solvent systems, and the CuTAPc-BPTA prepared with benzyl alcohol / dimethyl sulfoxide as the reaction system has the highest crystallinity.

[0096] Example 3: Optimization of Solvent Ratio

[0097] The ratio of benzyl alcohol / dimethyl sulfoxide mixed solvent in Example 1 was increased to (0:10), (1:9), (3:7), (5:5), (9:1) (v:v), while other ratios remained the same as in Example 2, to obtain copper phthalocyanine covalent organic framework material (CuTAPc-BPTA).

[0098] The obtained copper phthalocyanine covalent organic framework material (CuTAPc-BPTA) was subjected to performance testing, and the test results are as follows:

[0099] like Figure 6 The X-ray powder diffraction patterns show that CuTAPc-BPTA obtained with reaction systems of (0:10), (1:9), (3:7), (5:5), and (9:1) exhibits a low characteristic diffraction peak at 4.58°, indicating that CuTAPc-BPTA can be effectively prepared in benzyl alcohol / dimethyl sulfoxide solvent systems with volume ratios ranging from (0:10) to (9:1). However, CuTAPc-BPTA prepared with the benzyl alcohol / dimethyl sulfoxide (7:3, v:v) reaction system exhibits the highest crystallinity.

[0100] Example 4: Optimization of Reaction Temperature

[0101] The solvent was a benzyl alcohol / dimethyl sulfoxide mixed solvent (7:3). The reaction temperature was investigated at 60℃, 90℃ or 150℃, and other conditions were kept the same as in Example 3, to obtain the copper phthalocyanine covalent organic framework material (CuTAPc-BPTA).

[0102] The obtained copper phthalocyanine covalent organic framework material (CuTAPc-BPTA) was subjected to performance testing, and the test results are as follows:

[0103] like Figure 7 The X-ray powder diffraction pattern shows that CuTAPc-BPTA obtained by adjusting the reaction temperature to 60℃, 120℃ or 150℃ has a lower characteristic diffraction peak at 4.58°, indicating that CuTAPc-BPTA can be effectively prepared at reaction temperatures between 60-150℃, and the CuTAPc-BPTA obtained at a reaction temperature of 90℃ has the highest crystallinity.

[0104] Example 5: Optimization of Reaction Time

[0105] Based on Example 4, the effect of reaction time (2, 3, 5, 6, 7 days) was further investigated, while other factors remained the same, resulting in the copper phthalocyanine covalent organic framework material (CuTAPc-BPTA).

[0106] The obtained copper phthalocyanine covalent organic framework material (CuTAPc-BPTA) was subjected to performance testing, and the test results are as follows:

[0107] like Figure 8 The X-ray powder diffraction patterns show that CuTAPc-BPTA obtained by adjusting the reaction time to 2, 3, 5, 6, and 7 days exhibits a lower characteristic diffraction peak at 4.58°, indicating that CuTAPc-BPTA can be effectively prepared at reaction times ranging from 2 to 7 days, with the highest crystallinity obtained at a reaction time of 4 days.

[0108] Example 6: Preparation of CuTAPc-BPTA Composite Antibacterial Film

[0109] First, 6 mg of the CuTAPc-BPTA covalent organic framework powder prepared in Example 1 was added to 5 mL of deionized water and ultrasonically treated for 30 minutes to obtain a homogeneous suspension A. Simultaneously, 250 mg of CS was dissolved in 10 mL of an aqueous solution containing 1% acetic acid and stirred at 50°C for 1 hour to obtain a homogeneous solution B. Then, solutions A and B (CuTAPc-BPTA:CS) were mixed at a volume ratio of 1:2, and 160 μL of glycerol was added. Stirring continued until completely homogeneous, and the solution was ultrasonicated for 30 minutes to remove air bubbles. Then, 20 mL of the casting solution was slowly poured into a 9×9 cm petri dish and dried at 60°C for at least 18 hours until completely dry to obtain the CuTAPc-BPTA-CS composite membrane.

[0110] Example 7: Optimization of CS Ratio

[0111] In Example 6, the amount of CS was increased to 100, 150, and 200 mg, while other parameters remained the same as in Example 6. The film formation of the casting solutions with different CS ratios was observed, and the results are as follows:

[0112] When the dosage of CS is 250mg, a solid film is formed after drying. It is easy to peel off, has a smooth and flat surface, and is elastic and tough. However, when the dosage of CS is 100 or 150mg, it is not easy to form a film. When the dosage of CS is 200mg, a film can be formed, but the film has poor toughness.

[0113] Example 8: Application of CuTAPc-BPTA-CS Composite Antibacterial Film

[0114] The effect of the prepared CuTAPc-BPTA-CS composite film on fruit preservation was investigated.

[0115] Twelve fresh grapes of uniform size, free from pests and mechanical damage, were randomly divided into four groups: control group (no treatment), light-irradiated group (irradiated with a 650nm laser for 30 minutes), CuTAPc-BPTA-CS group (grapes wrapped in CuTAPc-BPTA-CS film), and CuTAPc-BPTA-CS + light-irradiated group (grapes wrapped in CuTAPc-BPTA-CS film and then irradiated with a 650nm laser for 30 minutes). After treatment, the grape samples were incubated at a constant temperature. The grape samples were photographed daily to record the surface condition.

[0116] like Figure 13As shown, the control group and the light-exposed group exhibited significant mold growth on the grape surface, with the degree of mold increasing over time. In contrast, the CuTAPc-BPTA-CS group showed only mild mold growth compared to the control and light-exposed groups. Furthermore, the grapes in the CuTAPc-BPTA-CS + light-exposed group appeared green, had sufficient moisture content, and exhibited high freshness, with no obvious mold growth. These results demonstrate that CuTAPc-BPTA-CS can exert a synergistic photodynamic / chemodynamic bactericidal effect, effectively inhibiting mold growth in grapes and extending their shelf life.

[0117] This invention constructs a covalent organic framework with photodynamic / chemodynamic bactericidal capabilities by using the photosensitizer 4,4',4”,4”'-tetra-(4-amino)copper phthalocyanine (CuTAPc) as a structural unit. The material has high crystallinity, and its regular structure restricts the distance between monomers, achieving a reduction in self-aggregation and quenching, thus improving the photodynamic effect. Its abundant active sites can complex copper ions, which consume glutathione (GSH) overexpressed in the bacterial microenvironment, avoiding the problem of reduced therapeutic efficacy due to GSH's scavenging of reactive oxygen species. Simultaneously, the Cu generated in the reaction... + This further triggers a Fenton-like reaction, generating chemodynamic therapeutic effects and compensating for the limited tissue penetration depth of light, which restricts the photodynamic bactericidal effect, thus achieving good therapeutic results on deep tissues. Furthermore, the crystal structure and abundant complexation sites of the covalent organic framework effectively avoid problems such as poisoning caused by copper ion leakage. This invention further prepares the organic framework material into a composite antibacterial membrane. The resulting composite antibacterial membrane (CuTAPc-BPTA-CS) can exert a synergistic photodynamic / chemodynamic bactericidal effect, effectively inhibiting mold growth in fruits and vegetables and extending shelf life. The covalent organic framework prepared in this invention also has broad application prospects in the fields of gas storage, catalysis, sensing, and separation.

[0118] It should be understood that the above detailed embodiments of this disclosure are merely illustrative or explanatory of the principles of this disclosure, and are not intended to limit the invention. Therefore, any modifications, equivalent substitutions, and improvements made within the spirit and principles of this disclosure should be included within the scope of protection of this invention.

Claims

1. A copper phthalocyanine covalent organic framework material having a synergistic bactericidal ability of photodynamic / chemical dynamic, characterized in that, has a structural unit shown in formula III; Formula III; The copper phthalocyanine covalent organic framework material is prepared by reacting an amino copper phthalocyanine compound shown in formula I and 2,5-bis(prop-2-yn-1-yloxy)benzene-dicarboxaldehyde; Formula I.

2. The method of producing a copper phthalocyanine covalent organic framework material according to claim 1, characterized in that, The method comprises the following steps: S1. The amino copper phthalocyanine compound, 2,5-bis(prop-2-yn-1-yloxy)benzene-dicarboxaldehyde and a solvent are uniformly mixed, and then a catalyst is uniformly added to obtain a reaction solution; S2. The reaction solution prepared in step S1 is reacted at 20-200 ℃ for 1-7 days; after the reaction is completed, centrifugal washing and drying are performed to obtain a copper phthalocyanine covalent organic framework.

3. The method for preparing the copper phthalocyanine covalent organic framework material according to claim 2, characterized in that, In step S1, the molar ratio of the amino copper phthalocyanine compound to 2,5-bis(prop-2-yn-1-yloxy)benzene-dicarboxaldehyde is 1: (2-6).

4. The method for preparing the copper phthalocyanine covalent organic framework material according to claim 2, wherein the solvent is selected from one or a combination of benzyl alcohol, dimethyl sulfoxide, dioxane, mesitylene, n-butanol and o-dichlorobenzene; And / or, the catalyst is an acid solution or a base solution.

5. The method for preparing the copper phthalocyanine covalent organic framework material according to claim 4, wherein the acid comprises one of acetic acid solution, p-toluenesulfonic acid solution, p-nitrobenzenesulfonic acid solution and trifluoroacetic acid solution; And / or, the base comprises one of sodium hydroxide solution and tetrahydro-pyrrole solution. In step S2, the reaction solution needs to be subjected to a freeze-nitrogen charging-vacuumizing-thawing cycle treatment before the reaction; N,N 6. The method for preparing the copper phthalocyanine covalent organic framework material according to claim 2, characterized in that, The copper phthalocyanine covalent organic framework material is further made into a copper phthalocyanine covalent organic framework composite antibacterial film; And / or, in step S2, the washing solvent is one or more of tetrahydrofuran, ethanol, acetonitrile, The method further comprises steps S3 and S4: - one or more of dimethylformamide.

7. The method for preparing the copper phthalocyanine covalent organic framework material according to claim 2, characterized in that, S3. The copper phthalocyanine covalent organic framework prepared in step S2 is dispersed in an aqueous solution to obtain a uniform solution A; chitosan is mixed with acetic acid solution, and stirring is performed at 25-60 ℃ to obtain a transparent solution B; S4. After solution A prepared in step S3 is mixed with solution B, glycerol is added, stirring is performed until uniform, gas bubbles in the solution are removed, a casting solution is obtained, and then the casting solution is cast into a film to obtain a copper phthalocyanine covalent organic framework composite antibacterial film. The mass concentration of the copper phthalocyanine covalent organic framework in step S3 is 0.3-1.8 mg / mL; And / or, in step S3, the mass concentration of the chitosan is 10-25 mg / mL.

8. The method of claim 7, wherein the copper phthalocyanine covalent organic framework is prepared by, The application includes, application in the preparation of photodynamic / chemical dynamic sterilization products; 9. Use of the copper phthalocyanine covalent organic framework material according to claim 1 or of the copper phthalocyanine covalent organic framework material produced according to the method of any one of claims 2 to 8, characterized in that or, application in fruit and vegetable preservation materials; or, application in the fields of gas storage, catalysis, sensing and separation. ​ ​

Images