Modified porphyrin MOFs, and methods of making and using the same

Abstract

The present application relates to the technical field of sonodynamic sterilization, further relates to a modified porphyrin MOF, a preparation method and application thereof. The modified porphyrin MOF is formed by introducing modified materials (triethylenediamine, 4,4'-dipyridyl, 1,4-di-(p-pyridyl)benzene) and metal ions and co-assembling with meso-tetra(4-carboxyphenyl)porphyrin, so that the ROS yield is significantly improved, and the technical problem of low ROS yield of porphyrin-based sonosensitizers in aqueous solution is solved.

Description

Technical Field

[0001] This invention relates to the field of sonodynamic sterilization technology, and more specifically, to a modified porphyrin MOF, its preparation method, and its application. Background Technology

[0002] Pasteurization, currently the most widely used sterilization method in the dairy industry, has a core technological advantage in that it uses a precisely controlled low-temperature sterilization process (typically 72-85℃ for 15-30 seconds). This process effectively inactivates major pathogenic bacteria in milk (including Salmonella, E. coli, Listeria, etc.) while maximizing the preservation of milk proteins, milk fat, water-soluble vitamins, and natural flavor compounds. However, pasteurization is a non-aseptic process, only achieving commercial sterility for pathogenic bacteria and not completely eliminating all microorganisms. This characteristic dictates that pasteurized milk must rely on a cold chain logistics system maintained at 2-6℃ throughout storage and distribution to inhibit the growth of residual microorganisms. This high dependence on the cold chain system significantly increases supply chain costs. Based on these industry pain points, developing new milk sterilization technologies has become an important research direction in the field of food science.

[0003] Sonodynamic sterilization (SDT) is an emerging sterilization strategy mediated by reactive oxygen species (ROS). Its core mechanism involves using low-intensity ultrasound (US) as an energy source to precisely activate sonosensitive agents, inducing a series of photophysical or photochemical processes that efficiently generate ROS. Simultaneously, the localized thermal effects and mechanical stress generated during ultrasound propagation synergistically damage bacterial structure and metabolic function with ROS, ultimately achieving the therapeutic goal of eliminating pathogens. Compared to traditional heat and chemical sterilization methods, SDT exhibits unique advantages: First, its non-thermal nature allows for sterilization at lower temperatures, effectively avoiding the destruction of nutrients (such as lactoferrin, immunoglobulins, and B vitamins) and natural flavor in milk during heat processing; second, the cavitation effect and penetrating power of ultrasound enable uniform processing of liquid foods, resulting in high sterilization efficiency; finally, the low toxicity of some sonosensitive agents (such as natural plant extracts) holds great potential in the food industry.

[0004] In sonodynamic sterilization, sonosensitive agents are considered a key factor directly affecting the effectiveness of sonodynamic sterilization (SDT). Porphyrin-based sonosensitive agents have high biocompatibility and have been approved for clinical medical research, showing promise for use in sonodynamic sterilization of milk. However, existing porphyrin-based sonosensitive agents are prone to inducing aggregation-induced quenching (ACQ) in aqueous solutions, resulting in low ROS yields in aqueous solutions.

[0005] Assembling porphyrins as organic ligands into porphyrin MOFs solved the ACQ effect caused by the close packing of porphyrin molecules, thus improving ROS yield to some extent. However, the ROS yield of porphyrin MOFs still needs to be improved. Summary of the Invention

[0006] To further improve the ROS yield of porphyrin-based sound-sensing agents in aqueous solutions, this invention provides a modified porphyrin MOF, its preparation method, and its application.

[0007] This invention significantly improves the ROS yield by introducing modified materials (triethylenediamine (DABCO), 4,4'-bipyridine (bpy), 1,4-bis(p-pyridyl)benzene (dpyb)) and metal ions to assemble with medium-tetra(4-carboxyphenyl)porphyrin (TCPP) to form modified porphyrin MOFs, thereby solving the technical problem of low ROS yield of porphyrin-based sound-sensing agents in aqueous solution.

[0008] One of the objectives of this invention is to provide a modified porphyrin MOF.

[0009] The modified porphyrin MOFs are selected from at least one of M-DABCO-TCPP, M-bpy-TCPP, and M-dpyb-TCPP; The chemical formula of M-DABCO-TCPP is C 54 H 24 N6O8M3; The chemical formula of the M-bpy-TCPP is C 58 H 33.75 N6O8M3; The chemical formula of the M-dpyb-TCPP is C 64 H 81 N6O9M3; M is selected from Zn, Ni or Cd.

[0010] The structural formula of the minimum asymmetric structural unit of M-DABCO-TCPP is: M2(M-TCPP)(DABCO).

[0011] As a preferred embodiment, the M-DABCO-TCPP is selected from Zn-DABCO-TCPP or Ni-DABCO-TCPP.

[0012] The powder X-ray diffraction of the Zn-DABCO-TCPP exhibits characteristic peaks at least at diffraction angles of 2θ = 7.4 ± 0.2°, 10.5 ± 0.2°, 12.7 ± 0.2°, 13.0 ± 0.2°, 15.0 ± 0.2°, 15.7 ± 0.2°, 19.8 ± 0.2°, 21.2 ± 0.2°, and 22.5 ± 0.2°.

[0013] The Zn-DABCO-TCPP belongs to the tetragonal crystal system. I-4 Space group; its cell parameters include: a=16.679Å, b=16.679Å, c=17.674Å, α=90°, β=90°, γ=90°.

[0014] The smallest asymmetric structural unit of Zn-DABCO-TCPP contains a fully deprotonated TCPP ligand, a DABCO ligand, and three divalent Zn ions. The three Zn ions have two different coordination configurations: Zn2 is hexacoordinate, coordinated to four pyrrole nitrogen atoms (N3) of the TCPP ligand and axially coordinated to a pyridine nitrogen atom; Zn1 is pentacoordinate, located at the center of an octahedral coordination configuration, coordinated to one pyridine nitrogen atom (N1) and four carboxyl oxygen atoms (O1) from different TCPP ligands. The planes of the DABCO and TCPP ligands form a 90° angle, and the two planes are 9.14 Å apart.

[0015] The powder X-ray diffraction of the Ni-DABCO-TCPP exhibits characteristic peaks at diffraction angles of at least 7.5±0.2°, 10.5±0.2°, 15.0±0.2°, 15.7±0.2°, 19.8±0.2°, and 21.2±0.2°.

[0016] The smallest asymmetric structural unit of Ni-DABCO-TCPP contains: a fully deprotonated TCPP ligand, a DABCO ligand, and three divalent Ni ions. The three Ni ions have two different coordination configurations: the Ni2 ion is hexacoordinate, coordinated with four pyrrole nitrogen atoms (N3) at the porphyrin center and axially coordinated with a pyridine nitrogen atom; the Ni1 ion is pentacoordinate, located at the center of an octahedral coordination configuration, coordinated with one pyridine nitrogen atom (N1) and four carboxyl oxygen atoms (O1) from different TCPP ligands. The DABCO ligand forms a 90° angle with the porphyrin plane, and the two planes are 9.14 Å apart.

[0017] The structural formula of the minimum asymmetric structural unit of M-bpy-TCPP is: M2(M-TCPP)(bpy).

[0018] As a preferred embodiment, the M-bpy-TCPP is Ni-bpy-TCPP.

[0019] The powder X-ray diffraction of the Ni-bpy-TCPP has characteristic peaks at least at diffraction angles of 2θ = 5.4 ± 0.2°, 7.6 ± 0.2°, 10.7 ± 0.2°, 12.0 ± 0.2°, 15.2 ± 0.2°, and 19.5 ± 0.2°.

[0020] The Ni-bpy-TCPP belongs to the tetragonal crystal system. P-4 Space group; its cell parameters include: a=16.6488Å, b=16.6488Å, c=16.6488Å, α=90°, β=90°, γ=90°.

[0021] The smallest asymmetric structural unit of Ni-bpy-TCPP contains a fully deprotonated TCPP ligand, a bpy ligand, and three Ni ions with two different coordination configurations: the Ni2 ion is tetracoordinated, coordinating with the four pyrrole nitrogen atoms (N2) of the TCPP ligand; the Ni1 ion is pentacoordinated, located at the center of the octahedral coordination configuration, coordinating with one pyridine nitrogen atom (N1) and four carboxyl oxygen atoms (O1) from different TCPP ligands. The planes of the bpy ligand and the TCPP ligand form an angle of 90°, and the distance between the two planes is 13.65 Å.

[0022] The structural formula of the minimum asymmetric structural unit of M-dpyb-TCPP is: M2(M-TCPP)(dpyb)(H2O).

[0023] As a preferred option, the M-dpyb-TCPP is selected from Cd-dpyb-TCPP or Ni-dpyb-TCPP.

[0024] The powder X-ray diffraction of the Cd-dpyb-TCPP exhibits characteristic peaks at diffraction angles of 2θ = 5.4 ± 0.2°, 7.6 ± 0.2°, 9.2 ± 0.2°, 10.3 ± 0.2°, 12.0 ± 0.2°, 13.5 ± 0.2°, and 15.2 ± 0.2°.

[0025] The Cd-dpyb-TCPP belongs to the triclinic crystal system. P-1 Space group; its cell parameters include: a=16.7839Å, b=17.0783Å, c=35.2154Å, α= 80.207°, β= 82.581°, γ= 89.872°.

[0026] The smallest asymmetric structural unit of Cd-dpyb-TCPP contains a fully deprotonated TCPP ligand, a dpyb ligand, a coordinated water molecule, and three divalent Cd ions. The three Cd ions have two different coordination configurations: Cd1 is five-coordinated, coordinating with four pyrrole nitrogen atoms (N1) of the TCPP ligand and an axially aligned oxygen atom (O), with the metal center slightly offset from the TCPP ligand plane, forming a near-pyramidal five-coordinate configuration; Cd2 is five-coordinated, located at the center of a deformed octahedral coordination configuration, coordinating with one pyridine nitrogen atom (N2) and four carboxyl oxygen atoms (O2) from different TCPP ligands. The angle between the dpyb ligand and the TCPP ligand plane is 49.78°. The distance between the two planes is 18.83 Å.

[0027] The powder X-ray diffraction of the Ni-dpyb-TCPP has characteristic peaks at least at diffraction angles of 5.4±0.2°, 7.6±0.2°, 9.2±0.2°, 10.4±0.2°, 12.0±0.2°, 13.5±0.2°, and 15.2±0.2°.

[0028] The smallest asymmetric structural unit of Ni-dpyb-TCPP contains a fully deprotonated TCPP ligand, a dpyb ligand, one coordinated water molecule, and three divalent Ni ions. The three Ni ions have two different coordination configurations: Ni1 is five-coordinated, coordinating with four pyrrole nitrogen atoms (N1) of the TCPP ligand and one oxygen atom (O) axially, with the metal center slightly offset from the TCPP ligand plane, forming a near-pyramidal five-coordinate coordination configuration; Ni2 is five-coordinated, located at the center of a deformed octahedral coordination configuration, coordinating with one pyridine nitrogen atom (N2) and four carboxyl oxygen atoms (O2) from different TCPP ligands. The angle between the dpyb ligand and the TCPP ligand plane is 49.78°. The distance between the two planes is 18.83 Å.

[0029] The modified porphyrin MOFs can be prepared from raw materials including metal salts, modifying materials, and methyl-tetra(4-carboxyphenyl)porphyrin using a hot solvent method. Since the nitrate ions in nitrates have extremely weak coordination ability and will not compete with metal ions for coordination sites, only nitrates can be used in this invention.

[0030] The second objective of this invention is to provide a method for preparing the modified porphyrin MOFs described in the first objective of this invention.

[0031] The preparation method of the modified porphyrin MOFs includes: 1) Dissolve the nitrate of M, the modified material, and the medium-tetra(4-carboxyphenyl)porphyrin in a solvent to obtain a mixed solution; M is selected from Zn, Ni, or Cd; 2) The mixed solution undergoes a hydrothermal reaction; 3) After the hydrothermal reaction is complete, cool down to room temperature and separate the solid product.

[0032] The nitrate of M is selected from one of Zn(NO3)2•6H2O, Ni(NO3)2•6H2O, and Cd(NO3)2•6H2O.

[0033] The modified material is selected from one of triethylenediamine (DABCO), 4,4'-bipyridine (bpy), and 1,4-bis(p-pyridyl)benzene (dpyb).

[0034] In the above method, the molar ratio of M nitrate, modified material, and methyl-tetra(4-carboxyphenyl)porphyrin can be 3:2:1 or approximately 3:2:1; for example (3±0.5):(2±0.5):(1±0.5), (3±0.4):(2±0.4):(1±0.4), (3±0.3):(2±0.3):(1±0.3), (3±0.2):(2±0.2):(1±0.2), (3±0.1):(2±0.1):(1±0.1).

[0035] The solvent is selected from at least one of N,N-dimethylformamide and anhydrous ethanol. Preferably, it contains N,N-dimethylformamide and anhydrous ethanol; the volume ratio of the two is preferably 5 to 1:1.

[0036] The amount of solvent used can be the standard amount.

[0037] The hydrothermal reaction temperature is 70~110℃; for example, 75℃, 78℃, 80℃, 82℃, 90℃, 95℃, 98℃, 100℃, 102℃, 105℃, 110℃.

[0038] The hydrothermal reaction time is 12 hours or more; for example, 20 hours, 23 hours, 24 hours, 25 hours, 26 hours, 30 hours, 32 hours, 33 hours, 34 hours, 36 hours, 48 ​​hours, or / and. The heating rate to the reaction temperature is 1~10℃ / min, for example 1℃ / min, 3℃ / min, 5℃ / min, 8℃ / min, 10℃ / min.

[0039] The cooling rate is 1~10℃ / min, for example 1℃ / min, 3℃ / min, 5℃ / min, 8℃ / min, 10℃ / min.

[0040] The nitrate of any of the above-mentioned M can be combined with any of the modifying materials to obtain different modified porphyrin MOFs.

[0041] As a preferred option, Zn-DABCO-TCPP was prepared using zinc nitrate, DABCO, and TCPP as ligands.

[0042] In the preparation method of Zn-DABCO-TCPP, the reaction temperature is controlled at 75~85℃ and the reaction time is controlled at 22~26h; otherwise, it is difficult to obtain Zn-DABCO-TCPP. Preferably, the reaction is carried out at 78~82℃ for 23~25h.

[0043] As a preferred option, Ni-bpy-TCPP was prepared using nickel nitrate, bpy, and TCPP as ligands.

[0044] In the preparation method of Ni-bpy-TCPP, the reaction temperature is controlled at 75~85℃ and the reaction time is controlled at 22~26h; otherwise, it is difficult to obtain Ni-bpy-TCPP. Preferably, the reaction is carried out at 78~82℃ for 23~25h.

[0045] As a preferred option, Cd-dpyb-TCPP was prepared using cadmium nitrate, dpyb, and TCPP as ligands.

[0046] In the preparation method of Cd-dpyb-TCPP, the reaction temperature is controlled at 95~105℃ and the reaction time is controlled at 31~35h; otherwise, it is difficult to obtain Cd-dpyb-TCPP. Preferably, the reaction is carried out at 98~102℃ for 32~34h.

[0047] As a preferred option, Ni-DABCO-TCPP was prepared using nickel nitrate, DABCO, and TCPP as ligands.

[0048] In the preparation method of Ni-DABCO-TCPP, the reaction temperature is controlled at 75~85℃ and the reaction time is controlled at 22~26h; otherwise, it is difficult to obtain Ni-DABCO-TCPP. Preferably, the reaction is carried out at 78~82℃ for 23~25h.

[0049] As a preferred option, Ni-dpyb-TCPP was prepared using nickel nitrate, dpyb, and TCPP as ligands.

[0050] In the preparation method of Ni-dpyb-TCPP, the reaction temperature is controlled at 95~105℃ and the reaction time is controlled at 31~35h; otherwise, it is difficult to obtain Ni-dpyb-TCPP. Preferably, the reaction is carried out at 98~102℃ for 32~34h.

[0051] A third objective of this invention is to provide the application of the modified porphyrin MOFs described in the first objective of the invention, or the modified porphyrin MOFs prepared by the preparation method described in the second objective of the invention, in the field of sonodynamic sterilization.

[0052] Compared with the prior art, the beneficial effects of the present invention are as follows: The Zn-DABCO-TCPP disclosed in this invention has a high superoxide anion (•O2) content. - The amount generated, using •O2 - The principle that can decolorize tetrazolium nitric acid (NBT) molecules is used to evaluate the •O2 content of Zn-DABCO-TCPP through NBT degradation experiments. - The results showed that after five minutes of ultrasound, the degradation rate was approximately 51%.

[0053] The Zn-DABCO-TCPP disclosed in this invention has a high singlet oxygen content ( 1 O2) generation amount, using 1 The principle that O2 can oxidize 1,3-diphenylisobenzofuran (DPBF) molecules, causing them to fade, is used to evaluate Zn-DABCO-TCPP through DPBF degradation experiments. 1 The results showed that after five minutes of sonication, the degradation rate of O2 was approximately 29%.

[0054] The Ni-bpy-TCPP disclosed in this invention has a high •O2 content. - Production amount, using •O2 - The principle that NBT molecules can be decolorized is used to evaluate the •O2 content of Ni-bpy-TCPP through NBT degradation experiments. - The results showed that after five minutes of ultrasound, the degradation rate was approximately 49%.

[0055] The Ni-bpy-TCPP disclosed in this invention has high performance. 1 O2 generation, using 1 The principle that O2 can oxidize DPBF molecules and cause them to fade can be used to evaluate Ni-bpy-TCPP through DPBF degradation experiments. 1 The results showed that after five minutes of sonication, the degradation rate of O2 was approximately 23%.

[0056] The Cd-dpyb-TCPP disclosed in this invention has a high •O2 content. - Production amount, using •O2 - The principle that NBT molecules can be decolorized is used to evaluate the •O2 content of Cd-dpyb-TCPP through NBT degradation experiments. - The results showed that after five minutes of ultrasound, the degradation rate was approximately 31%.

[0057] The Cd-dpyb-TCPP disclosed in this invention has high performance. 1 O2 generation, using 1 The principle that O2 can oxidize DPBF molecules and cause them to fade can be used to evaluate Cd-dpyb-TCPP through DPBF degradation experiments. 1 The results showed that after five minutes of sonication, the degradation rate of O2 was approximately 21%.

[0058] The Ni-DABCO-TCPP disclosed in this invention has a high superoxide anion (•O2) content. - The amount generated, using •O2 - The principle that it can decolorize tetrazolium nitro blue (NBT) molecules is used to evaluate the •O2 content of Ni-DABCO-TCPP through NBT degradation experiments. - The results showed that after five minutes of ultrasound, the degradation rate was approximately 69%.

[0059] The Ni-DABCO-TCPP disclosed in this invention has a high singlet oxygen content ( 1 O2) generation amount, using 1 The principle that O2 can oxidize 1,3-diphenylisobenzofuran (DPBF) molecules, causing them to fade, is used to evaluate Ni-DABCO-TCPP through DPBF degradation experiments. 1 The results showed that after five minutes of sonication, the degradation rate of O2 was approximately 31%.

[0060] The Ni-dpyb-TCPP disclosed in this invention has high •O2 content. - Production amount, using •O2 - The principle that NBT molecules can be decolorized is used to evaluate the •O2 content of Ni-dpyb-TCPP through NBT degradation experiments. - The results showed that after five minutes of ultrasound, the degradation rate was approximately 38%.

[0061] The Ni-dpyb-TCPP disclosed in this invention has high performance. 1 O2 generation, using 1 The principle that O2 can oxidize DPBF molecules and cause them to fade is used to evaluate Ni-dpyb-TCPP through DPBF degradation experiments. 1 The results showed that after five minutes of sonication, the degradation rate of O2 was approximately 26%. Attached Figure Description

[0062] Figure 1Here is a schematic diagram of the crystal structure of Zn-DABCO-TCPP; where A is a schematic diagram of the smallest structural unit of Zn-DABCO-TCPP, B is the arrangement of DABCO in Zn-DABCO-TCPP, and C is a schematic diagram of the framework structure of Zn-DABCO-TCPP. Figure 2 The XRD pattern and PXRD pattern of Zn-DABCO-TCPP are obtained from the simulation based on the crystal structure of Zn-DABCO-TCPP. Figure 3 The FT-IR plot of Zn-DABCO-TCPP; Figure 4 Here is a schematic diagram of the crystal structure of Ni-bpy-TCPP; where A is a schematic diagram of the smallest structural unit of Ni-bpy-TCPP, B is the arrangement of bpy in Ni-bpy-TCPP, and C is a schematic diagram of the framework structure of Ni-bpy-TCPP. Figure 5 The XRD pattern and PXRD pattern of Ni-bpy-TCPP are obtained from the simulation based on the Ni-bpy-TCPP crystal structure. Figure 6 The FT-IR plot of Ni-bpy-TCPP; Figure 7 The XRD pattern and PXRD pattern of Cd-dpyb-TCPP obtained from the simulation based on the crystal structure of Cd-dpyb-TCPP are shown. Figure 8 The FT-IR plot of Cd-dpyb-TCPP; Figure 9 PXRD pattern of Ni-DABCO-TCPP; Figure 10 The FT-IR plot of Ni-DABCO-TCPP; Figure 11 PXRD plot of Ni-dpyb-TCPP; Figure 12 The FT-IR plot of Ni-dpyb-TCPP; Figure 13 (A) is the UV absorption spectrum of NBT under Zn-TCPP+US, (B) is the UV absorption spectrum of NBT under Zn-DABCO-TCPP+US treatment, and (C) is the curve of characteristic absorbance of NBT in different systems as a function of ultrasonic time. Figure 14(A) is the UV absorption spectrum of NBT under Ni-TCPP+US, (B) is the UV absorption spectrum of NBT under Ni-bpy-TCPP+US treatment, and (C) is the curve of characteristic absorbance of NBT in different systems as a function of ultrasonic time. Figure 15 (A) is the UV absorption spectrum of NBT under Cd-TCPP+US, (B) is the UV absorption spectrum of NBT under Cd-dpyb-TCPP+US treatment, and (C) is the characteristic absorbance of NBT in different systems as a function of ultrasonic time. Figure 16 (A) is the UV absorption spectrum of NBT under Ni-TCPP+US, (B) is the UV absorption spectrum of NBT under Ni-DABCO-TCPP+US treatment, and (C) is the curve of characteristic absorbance of NBT in different systems as a function of ultrasonic time. Figure 17 (A) is the UV absorption spectrum of NBT under Ni-TCPP+US, (B) is the UV absorption spectrum of NBT under Ni-dpyb-TCPP+US treatment, and (C) is the curve of characteristic absorbance of NBT in different systems as a function of ultrasonic time. Figure 18 (A) is the UV absorption spectrum of DPBF under Zn-TCPP+US, (B) is the UV absorption spectrum of DPBF under Zn-DABCO-TCPP+US treatment, and (C) is the characteristic absorbance of DPBF in different systems as a function of ultrasonic time. Figure 19 (A) is the UV absorption spectrum of DPBF under Ni-TCPP+US, (B) is the UV absorption spectrum of DPBF under Ni-bpy-TCPP+US treatment, and (C) is the characteristic absorbance of DPBF in different systems as a function of ultrasonic time. Figure 20 (A) is the UV absorption spectrum of DPBF under Cd-TCPP+US, (B) is the UV absorption spectrum of DPBF under Cd-dpyb-TCPP+US treatment, and (C) is the characteristic absorbance of DPBF in different systems as a function of ultrasonic time. Figure 21 (A) is the UV absorption spectrum of DPBF under Ni-TCPP+US, (B) is the UV absorption spectrum of DPBF under Ni-DABCO-TCPP+US treatment, and (C) is the characteristic absorbance of DPBF in different systems as a function of ultrasonic time. Figure 22(A) is the UV absorption spectrum of DPBF under Ni-TCPP+US, (B) is the UV absorption spectrum of DPBF under Ni-dpyb-TCPP+US treatment, and (C) is the characteristic absorbance of DPBF in different systems as a function of ultrasonic time. Detailed Implementation

[0063] The present invention will now be described in detail with reference to the accompanying drawings and embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0064] All reagents used in the following examples and experimental cases are commercially available products.

[0065] The purity of Ni(NO3)2•6H2O is 99.99%, manufactured by Tianjin Xinbote Chemical Co., Ltd. Zn(NO3)2•6H2O has a purity of 99.99% and is manufactured by Tianjin Xinbote Chemical Co., Ltd. The purity of Cd(NO3)2•6H2O is 99.99%, manufactured by Tianjin Xinbote Chemical Co., Ltd. Triethylenediamine (DABCO) has a purity of 99.9% and is manufactured by Anaiji (Shanghai) Pharmaceutical Chemical Co., Ltd. 4,4'-Bipyridine (bpy) with a purity of 99%, manufactured by Shanghai Maclean Biochemical Technology Co., Ltd. 1,4-(di-p-pyridyl)benzene (dpyb) has a purity of 99% and is manufactured by Shanghai Maclean Biochemical Technology Co., Ltd. The purity of tetra(4-carboxyphenyl)porphyrin (TCPP) is 98%, manufactured by Beijing Huawirui Chemical Technology Co., Ltd. N,N-dimethylformamide has a purity of 99.5% and is manufactured by Tianjin Xinbote Chemical Co., Ltd. Anhydrous ethanol is 99.5%, manufactured by Tianjin Xinbote Chemical Co., Ltd.

[0066] Example 1 Weigh 0.03 mmol of Zn(NO3)2•6H2O, 0.02 mmol of triethylenediamine (DABCO), and 0.01 mmol of TCPP into a 25 mL beaker. Then add 3 mL of N,N-dimethylformamide and 1 mL of anhydrous ethanol to the beaker. Place the beaker in an ultrasonic bath and sonicate for 20 min to ensure complete dissolution, obtaining a mixed solution. Transfer the mixed solution to a 25 mL polytetrafluoroethylene (PTFE) liner, then transfer the liner to a high-pressure reactor. Insulate the reactor at 3 °C for [time missing]. -1 The temperature was increased to 80℃ at a rising rate and reacted at 80℃ for 24 h. After the reaction, the temperature was lowered to room temperature at a rate of 5℃ / min, and the solid product was separated. The solid product was washed by centrifugation at 8000 r / min for 3 min with 8 mL of N,N-dimethylformamide and 8 mL of ethanol solution, respectively, until the supernatant was colorless. The supernatant was then dried under vacuum at 55℃ for 24 h to obtain purplish-black crystals. The purplish-black crystals prepared in this example were named Zn-DABCO-TCPP.

[0067] (1) Single-crystal X-ray diffraction (SC-XRD) of Zn-DABCO-TCPP was performed. Single-crystal samples of Zn-DABCO-TCPP were selected, and diffraction data were collected in the range of 2θ = 2.82°~56.72° using a MoKα radiation source (λ = 0.71073 Å) on a CCD surface detector diffractometer. The crystal temperature was stabilized at 296.15 K throughout the experiment using a constant temperature system. Then, the structure was analyzed and refined using the Olex2 software platform. The structure analysis was performed using the built-in olex2.solve program of the software and the charge flipping method was used to solve for the initial phase. The structure refinement was performed using its XL refinement package, and the atomic parameters and structure factor were optimized by the least squares method.

[0068] The crystal structure, principal unit cell parameters, partial bond lengths, and bond angles of Zn-DABCO-TCPP were obtained by single-crystal X-ray diffraction (SC-XRD). The principal unit cell parameters of Zn-DABCO-TCPP are shown in Table 1.1, partial bond lengths are shown in Table 1.2, partial bond angles are shown in Table 1.3, and the crystal structure is shown in Table 1.4. Figure 1 As shown. Figure 1 In the diagram, A is a schematic diagram of the smallest structural unit of Zn-DABCO-TCPP, B is the arrangement of DABCO in Zn-DABCO-TCPP, and C is a schematic diagram of the framework structure of Zn-DABCO-TCPP.

[0069] Table 1.1 Main unit cell parameters of Zn-DABCO-TCPP

[0070] Table 1.2 Partial bond lengths of Zn-DABCO-TCPP

[0071] Table 1.3 Partial Bond Angles of Zn-DABCO-TCPP

[0072] Table 1.2, Table 1.3, Figure 1 In this diagram, the numbers following each element symbol are only used to distinguish the different coordination environments of the corresponding atom (or ion); different numbers indicate that the corresponding atom (or ion) is in different coordination environments. For example, the Zn2 ion is six-coordinated, coordinated with the four pyridine nitrogen atoms (N3) of the TCPP ligand and the nitrogen atom (N2) on the DABCO ligand. The Zn1 ion is five-coordinated, located at the center of the octahedral coordination configuration, coordinated with one pyridine nitrogen atom (N1) and four carboxyl oxygen atoms (O1) from different TCPP ligands.

[0073] The XRD pattern obtained from the simulation using the resolved Zn-DABCO-TCPP structure is shown below. Figure 2 As shown.

[0074] (2) Powder X-ray diffraction (PXRD) was performed on the Zn-DABCO-TCPP crystal.

[0075] PXRD conditions: Device: Anton Paar XRDynamic 500; X-rays used: Cu-Kα rays; Strength: 40 kV, 30 mA; Angle: 2θ = 5~50°; Scanning speed: 5° / min.

[0076] The PXRD of Zn-DABCO-TCPP is as follows: Figure 2 As shown.

[0077] Figure 2 The results show that Zn-DABCO-TCPP has characteristic peaks at least at diffraction angles of 2θ = 7.4 ± 0.2°, 10.5 ± 0.2°, 12.7 ± 0.2°, 13.0 ± 0.2°, 15.0 ± 0.2°, 15.7 ± 0.2°, 19.8 ± 0.2°, 21.2 ± 0.2°, and 22.5 ± 0.2°.

[0078] contrast Figure 2The two curves show that the positions and relative intensities of the diffraction peaks are basically consistent. This indicates that the true structure of Zn-DABCO-TCPP is consistent with the structure obtained from the analysis.

[0079] (3) The Zn-DABCO-TCPP crystal was subjected to infrared spectroscopy (FT-IR).

[0080] FT-IR measurement conditions: Instrument: Perkinelmer Spectrum Two; Scanning range: 400~4000 cm -1 ; Resolution: 4 cm -1 ; Number of scans: 64; ATR method (diamond crystal).

[0081] Zn-DABCO-TCPP's FT-IR, such as Figure 3 As shown.

[0082] Example 2 Weigh 0.03 mmol of Ni(NO3)2•6H2O, 0.02 mmol of 4,4'-bipyridine (bpy), and 0.01 mmol of TCPP into a 25 mL beaker. Then add 1.5 mL of N,N-dimethylformamide and 0.5 mL of anhydrous ethanol to the beaker. Place the beaker in an ultrasonic bath and sonicate for 20 min to ensure complete dissolution, obtaining a mixed solution. Transfer the mixed solution to a 25 mL polytetrafluoroethylene (PTFE) liner, then transfer the liner to a high-pressure reactor. Insulate the reactor at 3 °C for [time missing]. -1 The temperature was increased to 80℃ at a rising rate and reacted at 80℃ for 24 h. After the reaction, the temperature was decreased to room temperature at a rate of 5℃ / min, and the solid product was separated. The solid product was washed by centrifugation at 8000 r / min for 3 min with 8 mL of N,N-dimethylformamide and 8 mL of ethanol solution, respectively, until the supernatant was colorless. The supernatant was then dried under vacuum at 55℃ for 24 h to obtain purplish-black crystals. The purplish-black crystals prepared in this example were named Ni-bpy-TCPP.

[0083] (1) Single-crystal X-ray diffraction (SC-XRD) was performed on Ni-bpy-TCPP.

[0084] A single-crystal Ni-bpy-TCPP sample was selected, and diffraction data were collected in the range of 2θ = 2.82° to 56.72° using a MoKα radiation source (λ = 0.71073 Å) on a CCD surface detector diffractometer. The crystal temperature was stabilized at 296.15 K throughout the experiment using a constant temperature system. Subsequently, structural analysis and refinement were performed using the Olex2 software platform. Structural analysis utilized the built-in olex2.solve program and employed the charge-flipping method to solve for the initial phase. Structural refinement used its XL refinement package, optimizing atomic parameters and structure factors using the least squares method.

[0085] The crystal structure, principal unit cell parameters, partial bond lengths, and bond angles of Ni-bpy-TCPP were obtained by single-crystal X-ray diffraction (SC-XRD). The principal unit cell parameters of Ni-bpy-TCPP are shown in Table 2.1, partial bond lengths are shown in Table 2.2, partial bond angles are shown in Table 2.3, and the crystal structure is as follows: Figure 4 As shown. Figure 4 In the diagram, A is a schematic diagram of the smallest structural unit of Ni-bpy-TCPP, B is the arrangement of bpy in Ni-bpy-TCPP, and C is a schematic diagram of the framework structure of Ni-bpy-TCPP.

[0086] Table 2.1 Main cell parameters of Ni-bpy-TCPP

[0087] Table 2.2 Partial bond lengths of Ni-bpy-TCPP

[0088] Table 2.3 Partial Bond Angles of Ni-bpy-TCPP

[0089] Tables 2.2 and 2.3 Figure 4 In the diagram, the numbers following the element symbols are only used to distinguish the different coordination environments of the corresponding atoms; different numbers indicate that the corresponding atoms are in different coordination environments. For example, the Ni2 ion is tetracoordinated, coordinated with four pyrrole nitrogen atoms (N2) at the center of the porphyrin; the Ni1 ion is pentacoordinated, located at the center of an octahedral coordination configuration, coordinated with one pyridine nitrogen atom (N1) and four carboxyl oxygen atoms (O1) from different TCPP ligands. The XRD pattern obtained by simulation based on the resolved Ni-bpy-TCPP crystal structure is shown below. Figure 5 As shown.

[0090] (2) Powder X-ray diffraction (PXRD) was performed on the Ni-bpy-TCPP crystal.

[0091] PXRD conditions: Device: Anton Paar XRDynamic 500; X-rays used: Cu-Kα rays; Strength: 40 kV, 30 mA; Angle: 2θ = 5~50°; Scanning speed: 5° / min.

[0092] Ni-bpy-TCPP's PXRD is as follows Figure 5 As shown.

[0093] Figure 5 The results show that Ni-bpy-TCPP has characteristic peaks at least at diffraction angles of 2θ = 5.4 ± 0.2°, 7.6 ± 0.2°, 10.7 ± 0.2°, 12.0 ± 0.2°, 15.2 ± 0.2°, and 19.5 ± 0.2°.

[0094] contrast Figure 5 The two curves show that the positions and relative intensities of the diffraction peaks are basically consistent. This indicates that the actual structure of Ni-bpy-TCPP is consistent with the structure obtained from the analysis.

[0095] (3) The Ni-bpy-TCPP crystal was subjected to infrared spectroscopy (FT-IR).

[0096] FT-IR measurement conditions: Instrument: Perkinelmer Spectrum Two; Scanning range: 400~4000 cm -1 ; Resolution: 4 cm -1 ; Number of scans: 64; ATR method (diamond crystal).

[0097] Ni-bpy-TCPP's FT-IR, such as Figure 6 As shown.

[0098] Example 3 Weigh 0.03 mmol of Cd(NO3)2•6H2O, 0.02 mmol of 1,4-(di-p-pyridyl)benzene (dpyb), and 0.01 mmol of TCPP into a 25 mL beaker. Then add 2 mL of N,N-dimethylformamide and 2 mL of anhydrous ethanol to the beaker and sonicate for 20 min to ensure complete dissolution, obtaining a mixed solution. Transfer the mixed solution to a 25 mL polytetrafluoroethylene (PTFE) liner, then transfer the liner to a high-pressure reactor. Incubate the reactor at 3 °C for [time missing]. -1 The temperature was increased to 100℃ at a heating rate and reacted at 100℃ for 33 h. After the reaction was completed, the temperature was increased at 5℃·min. -1 The mixture was cooled to room temperature at a constant rate, and the solid product was separated and washed sequentially with 8 mL of N,N-dimethylformamide and 8 mL of ethanol solution in a centrifuge at 8000 r / min for 3 min until the supernatant was colorless. The supernatant was then dried under vacuum at 55 °C for 24 h to obtain purplish-black crystals. The purplish-black crystals prepared in this example were named Cd-dpyb-TCPP.

[0099] (1) Single-crystal X-ray diffraction (SC-XRD) was performed on Cd-dpyb-TCPP.

[0100] Single-crystal Cd-dpyb-TCPP samples were selected, and diffraction data were collected in the range of 2θ = 2.82° to 56.72° using a MoKα radiation source (λ = 0.71073 Å) on a CCD surface detector diffractometer. The crystal temperature was stabilized at 296.15 K throughout the experiment using a constant temperature system. Subsequently, structural analysis and refinement were performed using the Olex2 software platform. Structural analysis utilized the built-in olex2.solve program and employed the charge-flipping method to solve for the initial phase. Structural refinement used its XL refinement package, optimizing atomic parameters and structure factors using the least squares method.

[0101] The crystal structure, principal unit cell parameters, partial bond lengths, and bond angles of Cd-dpyb-TCPP were obtained by single-crystal X-ray diffraction (SC-XRD). The principal unit cell parameters of Cd-dpyb-TCPP are shown in Table 3.1, partial bond lengths are shown in Table 3.2, and partial bond angles are shown in Table 3.3.

[0102] Table 3.1 Main cell parameters of Cd-dpyb-TCPP

[0103] Table 3.2 Partial bond lengths of Cd-dpyb-TCPP

[0104] Table 3.3 Partial Bond Angles of Cd-dpyb-TCPP

[0105] In Tables 3.2 and 3.3, the numbers following the element symbols are only to distinguish the different coordination environments of the corresponding atoms; different numbers indicate that the corresponding atoms are in different coordination environments. For example, the Cd1 ion is five-coordinated, coordinated with four pyrrole nitrogen atoms (N1) at the center of the porphyrin, and coordinated with one oxygen atom (O1) at an axial position. The metal center is slightly deviated from the porphyrin plane, forming a five-coordinated near-pyramidal coordination configuration; the Cd2 ion is five-coordinated, located at the center of a deformed octahedral coordination configuration, coordinated with one pyridine nitrogen atom (N2) and four carboxyl oxygen atoms (O2) from different TCPP ligands.

[0106] The XRD pattern obtained from the simulation based on the resolved Cd-dpyb-TCPP crystal structure is shown below. Figure 7 As shown.

[0107] (2) Powder X-ray diffraction (PXRD) was performed on the Cd-dpyb-TCPP crystal.

[0108] PXRD conditions: Device: Anton Paar XRDynamic 500; X-rays used: Cu-Kα rays; Strength: 40 kV, 30 mA; Angle: 2θ = 5~50°; Scanning speed: 5° / min.

[0109] The PXRD of Cd-dpyb-TCPP is as follows: Figure 7 As shown.

[0110] Figure 7 The results show that Cd-dpyb-TCPP has characteristic peaks at least at diffraction angles of 2θ = 5.4 ± 0.2°, 7.6 ± 0.2°, 9.2 ± 0.2°, 10.4 ± 0.2°, 12.0 ± 0.2°, 13.5 ± 0.2°, and 15.2 ± 0.2°.

[0111] contrast Figure 7 The two curves show that the positions and relative intensities of the diffraction peaks are basically consistent. This indicates that the actual structure of Cd-dpyb-TCPP is consistent with the structure obtained from the analysis.

[0112] (3) The Cd-dpyb-TCPP crystal was subjected to infrared spectroscopy (FT-IR).

[0113] FT-IR measurement conditions: Instrument: Perkinelmer Spectrum Two; Scanning range: 400~4000 cm -1 ; Resolution: 4 cm -1 ; Number of scans: 64; ATR method (diamond crystal).

[0114] Cd-dpyb-TCPP's FT-IR, such as Figure 8 As shown.

[0115] Example 4 Weigh 0.03 mmol of Ni(NO3)2•6H2O, 0.02 mmol of triethylenediamine (DABCO), and 0.01 mmol of TCPP and add them to a 25 mL beaker. Then add 3 mL of N,N-dimethylformamide and 1 mL of anhydrous ethanol to the beaker, and sonicate the beaker for 20 min to fully dissolve the substances, obtaining a mixed solution. Transfer the mixed solution to a 25 mL polytetrafluoroethylene liner, transfer the liner to a high-pressure reactor, and incubate the reactor at 3 °C for 1 min. -1 The temperature was increased to 80℃ at a rising rate and reacted at 80℃ for 24 h. After the reaction, the temperature was decreased to room temperature at a rate of 5℃ / min, and the solid product was separated. The solid product was washed by centrifugation at 8000 r / min for 3 min with 8 mL of N,N-dimethylformamide and 8 mL of ethanol solution, respectively, until the supernatant was colorless. The supernatant was then dried under vacuum at 55℃ for 24 h to obtain purplish-black crystals. The purplish-black crystals prepared in this example were named Ni-DABCO-TCPP.

[0116] (1) Powder X-ray diffraction (PXRD) was performed on Ni-DABCO-TCPP crystal.

[0117] PXRD conditions: Device: Anton Paar XRDynamic 500; X-rays used: Cu-Kα rays; Strength: 40 kV, 30 mA; Angle: 2θ = 5~50°; Scanning speed: 5° / min.

[0118] PXRD of Ni-DABCO-TCPP as follows Figure 9 As shown.

[0119] Figure 9The results show that Ni-DABCO-TCPP has characteristic peaks at least at diffraction angles of 2θ = 7.5 ± 0.2°, 10.5 ± 0.2°, 15.0 ± 0.2°, 15.7 ± 0.2°, 19.8 ± 0.2°, and 21.2 ± 0.2°.

[0120] (2) The Ni-DABCO-TCPP crystal was subjected to infrared spectroscopy (FT-IR).

[0121] FT-IR measurement conditions: Instrument: Perkinelmer Spectrum Two; Scanning range: 400~4000 cm -1 ; Resolution: 4 cm -1 ; Number of scans: 64; ATR method (diamond crystal).

[0122] FT-IR of Ni-DABCO-TCPP, such as Figure 10 As shown.

[0123] Example 5 Weigh 0.03 mmol of Ni(NO3)2•6H2O, 0.02 mmol of 1,4-(di-p-pyridyl)benzene (dpyb), and 0.01 mmol of TCPP into a 25 mL beaker. Then add 2 mL of N,N-dimethylformamide and 2 mL of anhydrous ethanol to the beaker and sonicate for 20 min to ensure complete dissolution, obtaining a mixed solution. Transfer the mixed solution to a 25 mL polytetrafluoroethylene (PTFE) liner, then transfer the liner to a high-pressure reactor. Incubate the reactor at 3 °C for [time missing]. -1 The temperature was increased to 100℃ at a heating rate and reacted at 100℃ for 33 h; after the reaction was completed, the temperature was increased at 5 ℃·min. -1 The mixture was cooled to room temperature at a constant rate, and the solid product was separated and washed sequentially with 8 mL of N,N-dimethylformamide and 8 mL of ethanol solution in a centrifuge at 8000 r / min for 3 min until the supernatant was colorless. The supernatant was then dried under vacuum at 55 °C for 24 h to obtain purplish-black crystals. The purplish-black crystals prepared in this example were named Ni-dpyb-TCPP.

[0124] (1) Powder X-ray diffraction (PXRD) was performed on Ni-dpyb-TCPP crystal.

[0125] PXRD conditions: Device: Anton Paar XRDynamic 500; X-rays used: Cu-Kα rays; Strength: 40 kV, 30 mA; Angle: 2θ = 5~50°; Scanning speed: 5° / min.

[0126] Ni-dpyb-TCPP PXRD such as Figure 11 As shown.

[0127] Figure 11 The results show that Ni-dpyb-TCPP has characteristic peaks at least at diffraction angles of 2θ = 5.4 ± 0.2°, 7.6 ± 0.2°, 9.2 ± 0.2°, 10.4 ± 0.2°, 12.0 ± 0.2°, 13.5 ± 0.2°, and 15.2 ± 0.2°.

[0128] (2) The Ni-DABCO-TCPP crystal was subjected to infrared spectroscopy (FT-IR).

[0129] FT-IR measurement conditions: Instrument: Perkinelmer Spectrum Two; Scanning range: 400~4000 cm -1 ; Resolution: 4 cm -1 ; Number of scans: 64; ATR method (diamond crystal).

[0130] FT-IR of Ni-DABCO-TCPP, such as Figure 12 As shown.

[0131] Comparative Example 1 Weigh 0.1 mmol of Zn(NO3)2•6H2O and 0.02 mmol of TCPP and add them to a 25 mL beaker. Add 3 mL of N,N-diethylformamide solution and 1 mL of H2O to the beaker, and sonicate the beaker for 20 min to fully dissolve the solution and form a precipitate-free solution. Transfer the solution to a 25 mL polytetrafluoroethylene liner, place the liner in a 25 mL stainless steel reactor, and incubate the reactor at 5 °C for 1 min. -1 The temperature was increased to 85 °C at a controlled heating rate, held at 85 °C for 48 h, and then allowed to cool naturally to room temperature. The resulting precipitate was washed sequentially with N,N-diethylformamide solution and H2O by centrifugation until the supernatant was colorless. Finally, the product was dried in a vacuum drying oven at 55 °C for 12 h to obtain a purple solid powder sample. The purple solid powder sample prepared in this comparative example was named Zn-TCPP.

[0132] Comparative Example 2 Weigh 0.1 mmol of Ni(NO3)2•6H2O and 0.02 mmol of TCPP and add them to a 25 mL beaker. Add 3 mL of N,N-diethylformamide solution and 1 mL of H2O to the beaker, and sonicate the beaker for 20 min to allow it to dissolve completely and form a precipitate-free solution. Transfer the solution to a 25 mL polytetrafluoroethylene liner, place the liner into a 25 mL stainless steel reactor, and incubate the reactor at 5 °C for 1 min. -1 The temperature was increased to 85 °C at a controlled heating rate, held at 85 °C for 48 h, and then allowed to cool naturally to room temperature. The resulting precipitate was washed sequentially with N,N-diethylformamide solution and H2O by centrifugation until the supernatant was colorless. Finally, the product was dried in a vacuum drying oven at 55 °C for 12 h to obtain a purple solid powder sample. The purple solid powder sample prepared in this comparative example was named Ni-TCPP.

[0133] Comparative Example 3 Weigh 0.1 mmol of Cd(NO3)2•6H2O and 0.02 mmol of TCPP and add them to a 25 mL beaker; add 3 mL of N,N-diethylformamide solution and 1 mL of H2O to the beaker, and sonicate the beaker for 20 min to allow it to fully dissolve and form a precipitate-free solution; transfer the solution to a 25 mL polytetrafluoroethylene liner, place the liner into a 25 mL stainless steel reactor, and incubate the reactor at 5 °C for 1 min. -1 The temperature was increased to 85 °C at a controlled heating rate, held at 85 °C for 48 h, and then allowed to cool naturally to room temperature. The resulting precipitate was washed sequentially with N,N-diethylformamide solution and H₂O by centrifugation until the supernatant was colorless. Finally, the product was dried in a vacuum drying oven at 55 °C for 12 h to obtain a purple solid powder sample. The purple solid powder sample prepared in this comparative example was named Cd-TCPP.

[0134] Experimental Example 1 •O2 - Free radical generation experiment: Using phosphate-buffered saline (PBS) at pH 7.4 as the solvent and nitrotetrazole blue chloride (NBT) as the solute, prepare 0.2 mg / mL solutions. -1 NBT solution.

[0135] Using phosphate-buffered saline (PBS) at pH 7.4 as the solvent and Zn-DABCO-TCPP prepared in Example 1 as the solute, a 0.1 mg / mL solution was prepared. -1 MOF-1 material solution.

[0136] Using phosphate-buffered saline (PBS) at pH 7.4 as the solvent and Zn-TCPP prepared in Comparative Example 1 as the solute, a 0.1 mg / mL solution was prepared. -1 Zn-TCPP material solution.

[0137] Using phosphate-buffered saline (PBS) at pH 7.4 as the solvent and Ni-bpy-TCPP prepared in Example 2 as the solute, a 0.1 mg / mL solution was prepared. -1 MOF-2 material solution.

[0138] Using phosphate-buffered saline (PBS) at pH 7.4 as the solvent and Ni-TCPP prepared in Comparative Example 2 as the solute, a 0.1 mg / mL solution was prepared. -1 Ni-TCPP material solution.

[0139] Using phosphate-buffered saline (PBS) at pH 7.4 as the solvent and Cd-dpyb-TCPP prepared in Example 3 as the solute, a 0.1 mg / mL solution was prepared. -1 MOF-3 material solution.

[0140] Using phosphate-buffered saline (PBS) at pH 7.4 as the solvent and Cd-TCPP prepared in Comparative Example 3 as the solute, a 0.1 mg / mL solution was prepared. -1 Cd-TCPP material solution.

[0141] Using phosphate-buffered saline (PBS) at pH 7.4 as the solvent and Ni-DABCO-TCPP prepared in Example 4 as the solute, a 0.1 mg / mL solution was prepared. -1 MOF-4 material solution.

[0142] Using phosphate-buffered saline (PBS) at pH 7.4 as the solvent and Ni-dpyb-TCPP prepared in Example 5 as the solute, a 0.1 mg / mL solution was prepared. -1 MOF-5 material solution.

[0143] The degradation effect of test materials on NBT under ultrasonic treatment was used to evaluate the O2 content in different systems. - The formation of free radicals.

[0144] 1. Zn-DABCO-TCPP and Zn-TCPP's •O2 - Free radical generation experiment 1) Zn-TCPP group: Take a 5 mL centrifuge tube, add 200 μL of the prepared NBT solution and 2 mL of Zn-TCPP material solution to the centrifuge tube, and sonicate (1.5 W cm⁻¹). -2The system was subjected to a 1 MHz, 50% duty cycle reaction for 1, 2, 3, 4, and 5 min, and the absorbance change at 280 nm was measured. 2) MOF-1 material group: Take a 5 mL centrifuge tube, add 200 μL of the prepared NBT solution and 2 mL of MOF-1 material solution to the centrifuge tube, and sonicate (1.5 W cm⁻¹). -2 The system was subjected to a 1 MHz, 50% duty cycle reaction for 1, 2, 3, 4, and 5 min, and the absorbance change at 280 nm was measured. The experimental results were plotted as a curve with wavelength (wavelength) on the x-axis and absorbance (absorbance) on the y-axis, as shown below. Figure 13 (A) Figure 13 As shown in (B).

[0145] Plot a curve with time (C / C0) on the x-axis and residual rate (C / C0) on the y-axis. For example... Figure 13 As shown in (C). Residual rate (C / C0) refers to the ratio of the remaining dye content to the initial content. Degradation rate = 1 - C / C0.

[0146] Figure 13 (A) shows that when Zn-TCPP and ultrasound are used together, the absorbance of the system at 280 nm decreases with increasing ultrasound time, but the decrease is not significant. That is, the combined effect of Zn-TCPP and ultrasound only produces a weak degradation effect on NBT. This indicates that Zn-TCPP can generate a small amount of •O2 under ultrasound. - Free radicals.

[0147] Figure 13 (B) shows that when Zn-DABCO-TCPP and ultrasound are used together, the absorbance of the system at 280 nm decreases significantly with increasing ultrasound time. This indicates that the combined action of Zn-DABCO-TCPP and ultrasound can significantly degrade NBT. This suggests that Zn-DABCO-TCPP can generate a significant amount of •O2 under ultrasound. - Free radicals.

[0148] Figure 13 (C) shows that the 5-min degradation rate of Zn-TCPP was 13.8%, while that of Zn-DABCO-TCPP was 50.95%. Compared with Zn-TCPP, the 5-min degradation rate of Zn-DABCO-TCPP was significantly improved.

[0149] The degradation rate reflects the O2 - The yield of free radicals; the higher the degradation rate of NBT, the higher the O2 content.- The higher the free radical yield, the better. The statement "Compared to Zn-TCPP, the 5-min degradation rate of Zn-DABCO-TCPP is significantly improved" indicates that Zn-DABCO-TCPP has a higher •O2 content than Zn-TCPP. - The yield of free radicals.

[0150] 2. Ni-bpy-TCPP and Ni-TCPP's O2 - Free radical generation experiment 1) Ni-TCPP group: Take a 5 mL centrifuge tube, add 200 μL of the prepared NBT solution and 2 mL of Ni-TCPP material solution to the centrifuge tube, and sonicate (1.5 W cm⁻¹). -2 The system was subjected to a 1 MHz, 50% duty cycle reaction for 1, 2, 3, 4, and 5 min, and the absorbance change at 280 nm was measured. 2) MOF-2 material group: Take a 5 mL centrifuge tube, add 200 μL of the prepared NBT solution and 2 mL of MOF-2 material solution to the centrifuge tube, and sonicate (1.5 W cm⁻¹). -2 The system was subjected to a 1 MHz, 50% duty cycle reaction for 1, 2, 3, 4, and 5 min, and the absorbance change at 280 nm was measured. The experimental results were plotted as a curve with wavelength (wavelength) on the x-axis and absorbance (absorbance) on the y-axis, as shown below. Figure 14 (A) Figure 14 As shown in (B).

[0151] Plot a curve with time (C / C0) on the x-axis and residual rate (C / C0) on the y-axis. For example... Figure 14 As shown in (C).

[0152] Figure 14 (A) shows that when Ni-TCPP and ultrasound are used together, the absorbance of the system at 280 nm decreases with increasing ultrasound time, but the decrease is not significant. That is, the combined effect of Ni-TCPP and ultrasound only produces a weak degradation effect on NBT. This indicates that Ni-TCPP can generate a small amount of •O2 under ultrasound. - Free radicals.

[0153] Figure 14(B) shows that when Ni-bpy-TCPP and ultrasound are used together, the absorbance of the system at 280 nm decreases significantly with increasing ultrasound time. This indicates that the combined action of Ni-bpy-TCPP and ultrasound can significantly degrade NBT. This suggests that Ni-bpy-TCPP can generate a significant amount of •O2 under ultrasound. - Free radicals.

[0154] Figure 14 (C) shows that the 5-min degradation rate of Ni-TCPP was 17.4%, while that of Ni-bpy-TCPP was 48.7%. Compared with Ni-TCPP, the 5-min degradation rate of Ni-bpy-TCPP was significantly improved.

[0155] The degradation rate reflects the O2 - The higher the free radical yield, the higher the degradation rate of NBT, indicating that •O2 - The higher the free radical yield, the better. The statement "Compared to Ni-TCPP, Ni-bpy-TCPP showed a significantly higher 5-minute degradation rate" indicates that Ni-bpy-TCPP has a higher O2 content than Ni-TCPP. - The yield of free radicals.

[0156] 3. Cd-dpyb-TCPP and Cd-TCPP's O2 - Free radical generation experiment 1) Cd-TCPP group: Take a 5 mL centrifuge tube, add 200 μL of the prepared NBT solution and 2 mL of Cd-TCPP material solution to the centrifuge tube, and sonicate (1.5 W cm⁻¹). -2 The system was subjected to a 1 MHz, 50% duty cycle reaction for 1, 2, 3, 4, and 5 min, and the absorbance change at 280 nm was measured. 2) MOF-3 material group: Take a 5 mL centrifuge tube, add 200 μL of the prepared NBT solution and 2 mL of MOF-3 material solution to the centrifuge tube, and sonicate (1.5 W cm⁻¹). -2 The system was subjected to a 1 MHz, 50% duty cycle reaction for 1, 2, 3, 4, and 5 min, and the absorbance change at 280 nm was measured. The experimental results were plotted as a curve with wavelength (wavelength) on the x-axis and absorbance (absorbance) on the y-axis, as shown below. Figure 15 (A) Figure 15 As shown in (B).

[0157] Plot a curve with time (C / C0) on the x-axis and residual rate (C / C0) on the y-axis. For example... Figure 15 As shown in (C).

[0158] Figure 15 (A) shows that when Cd-TCPP and ultrasound work together, the absorbance of the system at 280 nm decreases with increasing ultrasound time, but the decrease is not significant. That is, the combined effect of Cd-TCPP and ultrasound only produces a weak degradation effect on NBT. This indicates that Cd-TCPP can generate a small amount of •O2 under ultrasound. - Free radicals.

[0159] Figure 15 (B) shows that when Cd-dpyb-TCPP and ultrasound are used together, the absorbance of the system at 280 nm decreases significantly with increasing ultrasound time. This indicates that the combined action of Cd-dpyb-TCPP and ultrasound can significantly degrade NBT. This suggests that Cd-dpyb-TCPP can generate a significant amount of •O2 under ultrasound. - Free radicals.

[0160] Figure 15 (C) shows that the 5-minute degradation rate of Cd-TCPP was 10.44%, while that of Cd-dpyb-TCPP was 30.86%. Compared with Cd-TCPP, the 5-minute degradation rate of Cd-dpyb-TCPP was significantly improved.

[0161] The degradation rate reflects the O2 - The yield of free radicals; the higher the degradation rate of NBT, the higher the O2 content. - The higher the free radical yield, the better. The statement "Compared to Cd-TCPP, the 5-minute degradation rate of Cd-dpyb-TCP is significantly improved" indicates that Cd-dpyb-TCP has a higher •O2 content than Cd-TCPP. - The yield of free radicals.

[0162] 4. O2 of Ni-DABCO-TCPPP and Ni-TCPP - Free radical generation experiment 1) Ni-TCPP group: Take a 5 mL centrifuge tube, add 200 μL of the prepared NBT solution and 2 mL of Ni-TCPP material solution to the centrifuge tube, and sonicate (1.5 W cm⁻¹). -2 The system was subjected to a 1 MHz, 50% duty cycle reaction for 1, 2, 3, 4, and 5 min, and the absorbance change at 280 nm was measured. 2) MOF-4 material group: Take a 5 mL centrifuge tube, add 200 μL of the prepared NBT solution and 2 mL of MOF-4 material solution to the centrifuge tube, and sonicate (1.5 W cm⁻¹). -2 The system was subjected to a 1 MHz, 50% duty cycle reaction for 1, 2, 3, 4, and 5 min, and the absorbance change at 280 nm was measured. The experimental results were plotted as a curve with wavelength (wavelength) on the x-axis and absorbance (absorbance) on the y-axis, as shown below. Figure 16 (A) Figure 16 As shown in (B).

[0163] Plot a curve with time (C / C0) on the x-axis and residual rate (C / C0) on the y-axis. For example... Figure 16 As shown in (C).

[0164] Figure 16 (A) shows that when Ni-TCPP and ultrasound are used together, the absorbance of the system at 280 nm decreases with increasing ultrasound time, but the decrease is not significant. That is, the combined effect of Ni-TCPP and ultrasound only produces a weak degradation effect on NBT. This indicates that Ni-TCPP can generate a small amount of •O2 under ultrasound. - Free radicals.

[0165] Figure 16 (B) The combined effect of Ni-DABCO-TCPP and ultrasound shows a significant decrease in absorbance at 280 nm with increasing ultrasound duration. This indicates that the combined action of Ni-DABCO-TCPP and ultrasound can significantly degrade NBT. This suggests that Ni-DABCO-TCPP can generate a significant amount of •O2 under ultrasound. - Free radicals.

[0166] Figure 16 (C) shows that the 5-min degradation rate of Ni-TCPP was 17.4%, while that of Ni-DABCO-TCPP was 68.1%. Compared with Ni-TCPP, the 5-min degradation rate of Ni-DABCO-TCPP was significantly improved.

[0167] The degradation rate reflects the O2 - The higher the free radical yield, the higher the degradation rate of NBT, indicating that •O2 - The higher the free radical yield, the better. The statement "Compared to Ni-TCPP, the 5-min degradation rate of Ni-DABCO-TCPP is significantly improved" indicates that Ni-DABCO-TCPP has a higher O2 content than Ni-TCPP. -The yield of free radicals.

[0168] 5. Ni-dpyb-TCPP and Ni-TCPP's O2 - Free radical generation experiment 1) Ni-TCPP group: Take a 5 mL centrifuge tube, add 200 μL of the prepared NBT solution and 2 mL of Ni-TCPP material solution to the centrifuge tube, and sonicate (1.5 W cm⁻¹). -2 The system was subjected to a 1 MHz, 50% duty cycle reaction for 1, 2, 3, 4, and 5 min, and the absorbance change at 280 nm was measured. 2) MOF-5 material group: Take a 5 mL centrifuge tube, add 200 μL of the prepared NBT solution and 2 mL of MOF-5 material solution to the centrifuge tube, and sonicate (1.5 W cm⁻¹). -2 The system was subjected to a 1 MHz, 50% duty cycle reaction for 1, 2, 3, 4, and 5 min, and the absorbance change at 280 nm was measured. The experimental results were plotted as a curve with wavelength (wavelength) on the x-axis and absorbance (absorbance) on the y-axis, as shown below. Figure 17 (A) Figure 17 (B) Figure 17 As shown in (C).

[0169] Figure 17 (A) shows that when Ni-TCPP and ultrasound are used together, the absorbance of the system at 280 nm decreases with increasing ultrasound time, but the decrease is not significant. That is, the combined effect of Ni-TCPP and ultrasound only produces a weak degradation effect on NBT. This indicates that Ni-TCPP can generate a small amount of •O2 under ultrasound. - Free radicals.

[0170] Figure 17 (B) shows that when Ni-dpyb-TCPP and ultrasound are used together, the absorbance of the system at 280 nm decreases significantly with increasing ultrasound time. This indicates that the combined action of Ni-dpyb-TCPP and ultrasound can significantly degrade NBT. This suggests that Ni-dpyb-TCPP can generate a significant amount of •O2 under ultrasound. - Free radicals.

[0171] Figure 17(C) shows that the 5-min degradation rate of Ni-TCPP was 17.4%, while that of Ni-dpyb-TCPP was 38%. Compared with Ni-TCPP, the 5-min degradation rate of Ni-dpyb-TCPP was significantly improved.

[0172] The degradation rate reflects the O2 - The higher the free radical yield, the higher the degradation rate of NBT, indicating that •O2 - The higher the free radical yield, the better. The statement "Compared to Ni-TCPP, Ni-dpyb-TCPP showed a significantly higher 5-minute degradation rate" indicates that Ni-dpyb-TCPP has a higher •O2 content than Ni-TCPP. - The yield of free radicals.

[0173] Experimental Example 2 1 O2 free radical generation experiment: Using phosphate-buffered saline (PBS) at pH 7.4 as the solvent and 1,3-diphenylisobenzofuran (DPBF) as the solute, prepare 0.27 mg / mL solutions. -1 DPBF solution.

[0174] The MOF-1 material solution, Zn-TCPP material solution, MOF-2 material solution, Ni-TCPP material solution, MOF-3 material solution, Cd-TCPP material solution, MOF-4 material solution, and MOF-5 material solution prepared in Experimental Example 1 were used.

[0175] The degradation effect of test materials on DPBF under ultrasonic irradiation was used to evaluate the degradation effect of DPBF in different systems. 1 The formation of O2 free radicals: 1. Zn-DABCO-TCPP and Zn-TCPP 1 Experiment on the generation of O2 free radicals 1) Zn-TCPP group: Take a 5 mL centrifuge tube, add 200 μL of the prepared DPBF solution and 2 mL of Zn-TCPP solution to the centrifuge tube, and sonicate (1.5 W cm⁻¹). -2 The system was subjected to a 1 MHz, 50% duty cycle reaction for 1, 2, 3, 4, and 5 min, and the absorbance change at 410 nm was measured. 2) MOF-1 material group: Take a 5 mL centrifuge tube, add 200 μL of the prepared DPBF solution and 2 mL of MOF-1 material solution to the centrifuge tube, and sonicate (1.5 W cm⁻¹). -2The system was subjected to a 1 MHz, 50% duty cycle reaction for 1, 2, 3, 4, and 5 min, and the absorbance change at 410 nm was measured. The experimental results were plotted as a curve with wavelength (wavelength) on the x-axis and absorbance (absorbance) on the y-axis, as shown below. Figure 18 (A) Figure 18 As shown in (B).

[0176] Plot a curve with time (C / C0) on the x-axis and residual rate (C / C0) on the y-axis. For example... Figure 18 As shown in (C).

[0177] Figure 18 (A) shows that when Zn-TCPP and ultrasound are used together, the absorbance of the system at 410 nm decreases with increasing ultrasound time, but the decrease is not significant. That is, the combined effect of Zn-TCPP and ultrasound only produces a weak degradation effect on DPBF. This indicates that Zn-TCPP can produce a small amount of degradation under ultrasound. 1 O2 free radicals.

[0178] Figure 18 (B) shows that when Zn-DABCO-TCPP and ultrasound are used together, the absorbance of the system at 410 nm decreases significantly with increasing ultrasound time. This indicates that the combined action of Zn-DABCO-TCPP and ultrasound can significantly degrade DPBF. This suggests that Zn-DABCO-TCPP can produce more [degradation] under ultrasound. 1 O2 free radicals.

[0179] Figure 18 (C) shows that the 5-min degradation rate of Zn-TCPP was 5.7%, while that of Zn-DABCO-TCPP was 29.03%. Compared with Zn-TCPP, the 5-min degradation rate of Zn-DABCO-TCPP was significantly improved.

[0180] Degradation rate reflects 1 The yield of O2 free radicals; the higher the degradation rate of DPBF, the better. 1 The higher the yield of O2 free radicals, the better. The statement "Compared to Zn-TCPP, Zn-DABCO-TCPP showed a significantly higher 5-minute degradation rate" indicates that Zn-DABCO-TCPP has higher... 1 Yield of O2 free radicals.

[0181] 2. Ni-bpy-TCPP and Ni-TCPP 1 Experiment on the generation of O2 free radicals 1) Ni-TCPP group: Take a 5 mL centrifuge tube, add 200 μL of the prepared DPBF solution and 2 mL of Ni-TCPP solution to the centrifuge tube, and sonicate (1.5 W cm⁻¹). -2 The system was subjected to a 1 MHz, 50% duty cycle reaction for 1, 2, 3, 4, and 5 min, and the absorbance change at 410 nm was measured. 3) MOF-2 material group: Take a 5 mL centrifuge tube, add 200 μL of the prepared DPBF solution and 2 mL of MOF-2 material solution to the centrifuge tube, and sonicate (1.5 W cm⁻¹). -2 The system was subjected to a 1 MHz, 50% duty cycle reaction for 1, 2, 3, 4, and 5 min, and the absorbance change at 410 nm was measured. The experimental results were plotted as a curve with wavelength (wavelength) on the x-axis and absorbance (absorbance) on the y-axis, as shown below. Figure 19 (A) Figure 19 As shown in (B).

[0182] Plot a curve with time (C / C0) on the x-axis and residual rate (C / C0) on the y-axis. For example... Figure 19 As shown in (C).

[0183] Figure 19 (A) shows that when Ni-TCPP and ultrasound are used together, the absorbance of the system at 410 nm decreases with increasing ultrasound time, but the decrease is not significant. That is, the combined effect of Ni-TCPP and ultrasound only produces a weak degradation effect on DPBF. This indicates that Ni-TCPP can produce a small amount of degradation under ultrasound. 1 O2 free radicals.

[0184] Figure 19 (B) shows that when Ni-bpy-TCPP and ultrasound are used together, the absorbance of the system at 410 nm decreases significantly with increasing ultrasound time. This indicates that the combined action of Ni-bpy-TCPP and ultrasound can significantly degrade DPBF. This suggests that Ni-bpy-TCPP can produce more absorbance under ultrasound. 1 O2 free radicals.

[0185] Figure 19 (C) shows that the 5-min degradation rate of Ni-TCPP was 6.9%, while that of Ni-bpy-TCPP was 23.1%. Compared with Ni-TCPP, the 5-min degradation rate of Ni-bpy-TCPP was significantly improved.

[0186] Degradation rate reflects1 The yield of O2 free radicals; the higher the degradation rate of DPBF, the better. 1 The higher the yield of O2 free radicals, the better. The statement "Compared to Ni-TCPP, Ni-bpy-TCPP showed a significantly higher 5-minute degradation rate" indicates that Ni-bpy-TCPP has higher... 1 Yield of O2 free radicals.

[0187] 3. Cd-dpyb-TCPP and Cd-TCPP 1 Experiment on the generation of O2 free radicals 1) Cd-TCPP group: Take a 5 mL centrifuge tube, add 200 μL of the prepared DPBF solution and 2 mL of Cd-TCPP solution to the centrifuge tube, and sonicate (1.5 W cm⁻¹). -2 The system was subjected to a 1 MHz, 50% duty cycle reaction for 1, 2, 3, 4, and 5 min, and the absorbance change at 410 nm was measured. 3) MOF-3 material group: Take a 5 mL centrifuge tube, add 200 μL of the prepared DPBF solution and 2 mL of MOF-3 material solution to the centrifuge tube, and sonicate (1.5 W cm⁻¹). -2 The system was subjected to a 1 MHz, 50% duty cycle reaction for 1, 2, 3, 4, and 5 min, and the absorbance change at 410 nm was measured. The experimental results were plotted as a curve with wavelength (wavelength) on the x-axis and absorbance (absorbance) on the y-axis, as shown below. Figure 20 (A) Figure 20 As shown in (B).

[0188] Plot a curve with time (C / C0) on the x-axis and residual rate (C / C0) on the y-axis. For example... Figure 20 As shown in (C).

[0189] Figure 20 (A) shows that when Cd-TCPP and ultrasound are used together, the absorbance of the system at 410 nm decreases with increasing ultrasound time, but the decrease is not significant. That is, the combined effect of Cd-TCPP and ultrasound only produces a weak degradation effect on DPBF. This indicates that Cd-TCPP can produce a small amount of degradation under ultrasound. 1 O2 free radicals.

[0190] Figure 20(B) shows that when Cd-dpyb-TCPP and ultrasound are used together, the absorbance of the system at 410 nm decreases significantly with increasing ultrasound time. That is, the combined action of Cd-dpyb-TCPP and ultrasound can significantly degrade DPBF. This indicates that Cd-dpyb-TCPP can produce more [degradation] under ultrasound. 1 O2 free radicals.

[0191] Figure 20 (C) shows that the 5-minute degradation rate of Cd-TCPP was 7.2%, while that of Cd-dpyb-TCPP was 20.88%. Compared with Cd-TCPP, the 5-minute degradation rate of Cd-dpyb-TCPP was significantly improved.

[0192] Degradation rate reflects 1 The yield of O2 free radicals; the higher the degradation rate of DPBF, the better. 1 The higher the yield of O2 free radicals, the better. The statement "Compared to Cd-TCPP, Cd-dpyb-TCPP showed a significantly higher 5-minute degradation rate" indicates that Cd-dpyb-TCPP has a higher... 1 Yield of O2 free radicals.

[0193] 4. Ni-DABCO-TCPP and Ni-TCPP 1 Experiment on the generation of O2 free radicals 1) Ni-TCPP group: Take a 5 mL centrifuge tube, add 200 μL of the prepared DPBF solution and 2 mL of Ni-TCPP solution to the centrifuge tube, and sonicate (1.5 W cm⁻¹). -2 The system was subjected to a 1 MHz, 50% duty cycle reaction for 1, 2, 3, 4, and 5 min, and the absorbance change at 410 nm was measured. 3) MOF-4 material group: Take a 5 mL centrifuge tube, add 200 μL of the prepared DPBF solution and 2 mL of MOF-4 material solution to the centrifuge tube, and sonicate (1.5 W cm⁻¹). -2 The system was subjected to a 1 MHz, 50% duty cycle reaction for 1, 2, 3, 4, and 5 min, and the absorbance change at 410 nm was measured. The experimental results were plotted as a curve with wavelength (wavelength) on the x-axis and absorbance (absorbance) on the y-axis, as shown below. Figure 21 (A) Figure 21 As shown in (B).

[0194] Plot a curve with time (C / C0) on the x-axis and residual rate (C / C0) on the y-axis. For example... Figure 21 As shown in (C).

[0195] Figure 21 (A) shows that when Ni-TCPP and ultrasound are used together, the absorbance of the system at 410 nm decreases with increasing ultrasound time, but the decrease is not significant. That is, the combined effect of Ni-TCPP and ultrasound only produces a weak degradation effect on DPBF. This indicates that Ni-TCPP can produce a small amount of degradation under ultrasound. 1 O2 free radicals.

[0196] Figure 21 (B) shows that when Ni-DABCO-TCPP and ultrasound are used together, the absorbance of the system at 410 nm decreases significantly with increasing ultrasound time. That is, the combined action of Ni-DABCO-TCPP and ultrasound can significantly degrade DPBF. This indicates that Ni-DABCO-TCPP can produce more [degradation] under ultrasound. 1 O2 free radicals.

[0197] Figure 21 (C) shows that the 5-min degradation rate of Ni-TCPP was 6.9%, while that of Ni-DABCO-TCPP was 31.1%. Compared with Ni-TCPP, the 5-min degradation rate of Ni-DABCO-TCPP was significantly improved.

[0198] Degradation rate reflects 1 The yield of O2 free radicals; the higher the degradation rate of DPBF, the better. 1 The higher the yield of O2 free radicals, the better. The statement "Compared to Ni-TCPP, Ni-DABCO-TCPP showed a significantly higher 5-minute degradation rate" indicates that Ni-DABCO-TCPP has higher... 1 Yield of O2 free radicals.

[0199] 5. Ni-dpyb-TCPP and Ni-TCPP 1 Experiment on the generation of O2 free radicals 1) Ni-TCPP group: Take a 5 mL centrifuge tube, add 200 μL of the prepared DPBF solution and 2 mL of Ni-TCPP solution to the centrifuge tube, and sonicate (1.5 W cm⁻¹). -2 The system was subjected to a 1 MHz, 50% duty cycle reaction for 1, 2, 3, 4, and 5 min, and the absorbance change at 410 nm was measured. 3) MOF-5 material group: Take a 5 mL centrifuge tube, add 200 μL of the prepared DPBF solution and 2 mL of MOF-5 material solution to the centrifuge tube, and sonicate (1.5 W cm⁻¹). -2 The system was subjected to a 1 MHz, 50% duty cycle reaction for 1, 2, 3, 4, and 5 min, and the absorbance change at 410 nm was measured. The experimental results were plotted as a curve with wavelength (wavelength) on the x-axis and absorbance (absorbance) on the y-axis, as shown below. Figure 22 (A) Figure 22 As shown in (B).

[0200] Plot a curve with time (C / C0) on the x-axis and residual rate (C / C0) on the y-axis. For example... Figure 22 As shown in (C).

[0201] Figure 22 (A) shows that when Ni-TCPP and ultrasound are used together, the absorbance of the system at 410 nm decreases with increasing ultrasound time, but the decrease is not significant. That is, the combined effect of Ni-TCPP and ultrasound only produces a weak degradation effect on DPBF. This indicates that Ni-TCPP can produce a small amount of degradation under ultrasound. 1 O2 free radicals.

[0202] Figure 22 (B) shows that when Ni-dpyb-TCPP and ultrasound are used together, the absorbance of the system at 410 nm decreases significantly with increasing ultrasound time. That is, the combined effect of Ni-dpyb-TCPP and ultrasound can significantly degrade DPBF. This indicates that Ni-dpyb-TCPP can produce more [degradation] under ultrasound. 1 O2 free radicals.

[0203] Figure 22 (C) shows that the 5-min degradation rate of Ni-TCPP was 6.9%, while that of Ni-dpyb-TCPP was 26%. Compared with Ni-TCPP, the 5-min degradation rate of Ni-dpyb-TCPP was significantly improved.

[0204] Degradation rate reflects 1 The yield of O2 free radicals; the higher the degradation rate of DPBF, the better. 1 The higher the yield of O2 free radicals, the better. The statement "Compared to Ni-TCPP, Ni-dpyb-TCPP showed a significantly higher 5-minute degradation rate" indicates that Ni-dpyb-TCPP has higher... 1 Yield of O2 free radicals.

Claims

1. A modified porphyrin MOF, selected from at least one of M-DABCO-TCPP, M-bpy-TCPP, and M-dpyb-TCPP; The chemical formula of M-DABCO-TCPP is C 54 H 24 N6O8M3; The chemical formula of the M-bpy-TCPP is C 58 H 33.75 N6O8M3; The chemical formula of the M-dpyb-TCPP is C 64 H 81 N6O9M3; in, M is selected from Zn, Ni, or Cd.

2. The modified porphyrin MOFs as described in claim 1, characterized in that, The structural formula of the minimum asymmetric structural unit of M-DABCO-TCPP is: M2(M-TCPP)(DABCO); or / and, The structural formula of the minimum asymmetric structural unit of M-bpy-TCPP is: M2(M-TCPP)(bpy); or / and, The structural formula of the minimum asymmetric structural unit of M-dpyb-TCPP is: M2(M-TCPP)(dpyb)(H2O).

3. The modified porphyrin MOFs as described in claim 1, characterized in that, The M-DABCO-TCPP is Zn-DABCO-TCPP; the powder X-ray diffraction of the Zn-DABCO-TCPP exhibits characteristic peaks at least at diffraction angles of 2θ = 7.4 ± 0.2°, 10.5 ± 0.2°, 12.7 ± 0.2°, 13.0 ± 0.2°, 15.0 ± 0.2°, 15.7 ± 0.2°, 19.8 ± 0.2°, 21.2 ± 0.2°, and 22.5 ± 0.2°; or / and, The M-DABCO-TCPP is Ni-DABCO-TCPP; the powder X-ray diffraction of the Ni-DABCO-TCPP exhibits characteristic peaks at diffraction angles of at least 7.5±0.2°, 10.5±0.2°, 15.0±0.2°, 15.7±0.2°, 19.8±0.2°, and 21.2±0.2°; or / and, The M-bpy-TCPP is Ni-bpy-TCPP; the powder X-ray diffraction of the Ni-bpy-TCPP exhibits characteristic peaks at diffraction angles of at least 2θ = 5.4 ± 0.2°, 7.6 ± 0.2°, 10.7 ± 0.2°, 12.0 ± 0.2°, 15.2 ± 0.2°, and 19.5 ± 0.2°; or / and, The M-dpyb-TCPP is Cd-dpyb-TCPP; the powder X-ray diffraction of the Cd-dpyb-TCPP has characteristic peaks at least at diffraction angles of 2θ = 5.4 ± 0.2°, 7.6 ± 0.2°, 9.2 ± 0.2°, 10.3 ± 0.2°, 12.0 ± 0.2°, 13.5 ± 0.2°, and 15.2 ± 0.2°; or / and, The M-dpyb-TCPP is Ni-dpyb-TCPP; the powder X-ray diffraction of the Ni-dpyb-TCPP has characteristic peaks at least at diffraction angles of 5.4±0.2°, 7.6±0.2°, 9.2±0.2°, 10.4±0.2°, 12.0±0.2°, 13.5±0.2° and 15.2±0.2°.

4. The modified porphyrin MOFs as described in claim 1, characterized in that, The Zn-DABCO-TCPP has characteristic peaks at least at diffraction angles of 2θ = 19.8 ± 0.2°, 21.2 ± 0.2°, and 22.5 ± 0.2°.

5. The modified porphyrin MOFs as described in claim 1, characterized in that, The Zn-DABCO-TCPP belongs to the tetragonal crystal system. I-4 Space group; Its unit cell parameters include: a = 16.679 Å, b = 16.679 Å, c = 17.674 Å, α = 90°, β = 90°, γ = 90°; or / and, The Ni-bpy-TCPP belongs to the tetragonal crystal system. P-4 Space group; its cell parameters include: a = 16.6488 Å, b = 16.6488 Å, c = 16.6488 Å, α = 90°, β = 90°, γ = 90°; or / and, The Cd-dpyb-TCPP belongs to the triclinic crystal system. P-1 Space group; its cell parameters include: a=16.7839Å, b=17.0783Å, c=35.2154Å, α= 80.207°, β= 82.581°, γ= 89.872°.

6. A method for preparing the modified porphyrin MOFs according to any one of claims 1-5, comprising: 1) Dissolve the nitrate of M, the modified material, and the medium-tetra(4-carboxyphenyl)porphyrin in a solvent to obtain a mixed solution; 2) The mixed solution undergoes a hydrothermal reaction; 3) After the hydrothermal reaction is complete, cool down to room temperature and separate the solid product.

7. The preparation method according to claim 6, characterized in that, The nitrate of M is selected from one of Zn(NO3)2•6H2O, Ni(NO3)2•6H2O, and Cd(NO3)2•6H2O; or / and, The modified material is selected from one of triethylenediamine, 4,4'-bipyridine, and 1,4-bis(p-pyridyl)benzene; or / and, The solvent is selected from at least one of N,N-dimethylformamide and anhydrous ethanol.

8. The preparation method according to claim 6, characterized in that, include: The hydrothermal reaction temperature is 70~110℃; or / and, The hydrothermal reaction time is more than 12 hours; or / and, The heating rate to the reaction temperature is 1~10℃ / min; or / and, The cooling rate is 1~10℃ / min.

9. The preparation method according to claim 6, characterized in that, include: In the preparation method of Zn-DABCO-TCPP, the reaction temperature is controlled at 75~85℃ and the reaction time is controlled at 22~26h. In the preparation method of Ni-bpy-TCPP, the reaction temperature is controlled at 75~85℃ and the reaction time is controlled at 22~26h. In the preparation method of Cd-dpyb-TCPP, the reaction temperature is controlled at 95~105℃ and the reaction time is controlled at 31~35h; In the preparation method of Ni-DABCO-TCPP, the reaction temperature is controlled at 75~85℃ and the reaction time is controlled at 22~26h. In the preparation method of Ni-dpyb-TCPP, the reaction temperature is controlled at 95~105℃ and the reaction time is controlled at 31~35h.

10. The application of the modified porphyrin MOFs according to any one of claims 1-5 or the modified porphyrin MOFs prepared by the preparation method according to any one of claims 6-9 in the field of sonodynamic sterilization.

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