Yb-TCPP metal organic framework compound as well as preparation method and application thereof
The Yb-TCPP metal organic framework compound addresses the lack of dual functionalities in existing materials by enhancing near-infrared and photodynamic therapy capabilities, enabling efficient near-infrared imaging and photodynamic therapy through a tailored synthesis process.
Patent Information
- Application Number
- CN202411401700.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-09
- Publication Date
- 2024-12-27
AI Technical Summary
Existing rare earth metal porphyrin MOF materials lack both near-infrared luminescence and photodynamic therapy functions, limiting their multi-faceted synergistic applications.
A preparation method for a Yb-TCPP metal organic framework compound involving specific solvent ratios, reaction conditions, and cooling rates to synthesize a Yb-TCPP metal organic framework compound with a monoclinic structure, utilizing porphyrin as an antenna molecule to enhance near-infrared luminescence and promote singlet oxygen generation.
The synthesized Yb-TCPP MOF exhibits high near-infrared luminescence intensity and effective photodynamic therapy capabilities, with potential applications in near-infrared imaging and photodynamic therapy, and tracing material flow in propellant extrusion molding.
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Figure CN119192603A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of near-infrared imaging and photodynamic therapy, relates to rare earth metal organic framework compounds, and specifically relates to a Yb-TCPP metal organic framework compound, a preparation method and an application thereof. Background Art
[0002] The wavelength of near-infrared region is between 780nm-2526nm, and its penetrating ability is very strong, with small light scattering, small reflectivity, and little energy loss. Therefore, when near-infrared is used for biological imaging, there is less tissue absorption, less tissue autofluorescence, and strong tissue penetration. It is widely used in fiber optic communications, optical materials, biological imaging, etc. Rare earth metal ion Yb 3+ It has near-infrared luminescence properties and a long-lived excited state, and can be used as a near-infrared light source. However, its luminescence mode is usually ff transition, which does not conform to the spectral selection law. Therefore, the probability of transition from the ground state to the excited state is relatively low, resulting in its near-infrared luminescence intensity being relatively low. Therefore, a sensitizer (such as an antenna molecule) is required for sensitization.
[0003] Porphyrin is a class of organic compounds with large conjugated structures. Porphyrin molecules have high extinction coefficients and are very efficient in converting from the ground state to the excited state. The electron mobility within the porphyrin ring is large, and it can effectively absorb the energy of ultraviolet and visible light, and transition triplet oxygen in the ground state to the excited state to produce singlet oxygen. Singlet oxygen has a strong oxidizing ability. In the dominant photodynamic type II reaction, singlet oxygen is the main body of treatment. It has strong phototoxicity and has a good photodynamic therapy effect on hypoxic cancer cells.
[0004] Most of the existing rare earth metal porphyrin MOF materials use metal elements such as Zn\Cu\Ni\Al\Ca\Ag\Au as ligands, and most of the synthesized MOF materials have only one-sided applications such as fluorescence and photocatalysis. There are few reports on rare earth metal porphyrin MOF materials with excellent near-infrared luminescence performance, and even fewer studies on metal porphyrin MOF materials that can be used in conjunction with near-infrared luminescence and photodynamic therapy, which limits the multi-faceted synergistic application of metal porphyrin MOF. Summary of the invention
[0005] In view of the defects and shortcomings of the prior art, the purpose of the present invention is to provide a Yb-TCPP metal organic framework compound, a preparation method and its application, so as to solve the technical problem that the prior art lacks rare earth metal porphyrin MOF materials with both near-infrared luminescence and photodynamic therapy functions.
[0006] In order to solve the above technical problems, the present invention adopts the following technical solutions to achieve the above problems:
[0007] A preparation method of a Yb-TCPP metal organic framework compound is characterized in that the method comprises: dissolving 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin in N,N-dimethylacetamide to obtain a solution containing a porphyrin group compound; dissolving an ytterbium salt in an aqueous hydrochloric acid solution to obtain a metal precursor solution; transferring the solution containing the porphyrin group compound and the metal precursor solution to a reaction container, stirring, and then keeping the temperature at 110-140°C for 48-96h, and cooling at a rate of 5-10°C / h after heating to obtain the Yb-TCPP metal organic framework compound.
[0008] The present invention also has the following technical features:
[0009] Specifically, the molecular formula of the Yb-TCPP metal organic framework compound is Yb2O 24 H 100 N 14 C 114 , its crystals belong to the monoclinic system, P121 / c1 space group.
[0010] Specifically and preferably, the heating conditions are: heating temperature is 120° C., heating time is 72 h, and cooling at a rate of 5° C. / h after heating.
[0011] Specifically and preferably, the molar ratio of ytterbium in the 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin and ytterbium salt is 0.0125:0.025.
[0012] Specifically and preferably, the concentration of the aqueous hydrochloric acid solution is 2.2 mol / L, and the volume ratio of the aqueous hydrochloric acid solution to N,N-dimethylacetamide is 3.33:6.67.
[0013] Specifically, the ytterbium salt is YbCl3·6H2O.
[0014] Specifically, the temperature is lowered to 20-45° C. after the heating is completed.
[0015] Specifically, the stirring time is 10 to 20 minutes.
[0016] The present invention also protects the Yb-TCPP metal organic framework compound prepared by the preparation method of the Yb-TCPP metal organic framework compound as described above.
[0017] The present invention also protects the use of the Yb-TCPP metal organic framework compound described above for sensitizing singlet oxygen generation.
[0018] The beneficial technical effects of the present invention compared with the prior art are as follows:
[0019] (I) The Yb-TCPP metal organic framework compound synthesized by the present invention is a type of rare earth porphyrin metal organic framework compound, in which porphyrin as an antenna molecule promotes the near-infrared luminescence of the coordinated active metal Yb, and the coordinated metal ytterbium promotes the ability of the ligand porphyrin to excite the production of singlet oxygen. The two cooperate and promote each other, and can be applied to near-infrared imaging and photodynamic therapy at the same time. On the other hand, the near-infrared imaging properties of the MOF material make it have potential application prospects in the tracing of the flow state of materials in the field of propellant extrusion molding.
[0020] (II) The present invention uses N,N-dimethylformamide and hydrochloric acid aqueous solution as a mixed reaction solvent, selects a suitable reaction solvent ratio, reacts in a reactor, adjusts the stirring and dissolving time, reaction temperature, reaction time, cooling rate and other reaction conditions, and obtains purple flaky crystals after cooling to room temperature. The obtained crystals are washed, filtered and dried to obtain the target product. The preparation method of the present invention is simple, has a high yield (yield of more than 60%), and is easy to realize industrialization. BRIEF DESCRIPTION OF THE DRAWINGS
[0021] Figure 1 is the crystal structure of the Yb-TCPP metal organic framework compound in Example 1; Figure 1 In the figure, (a) is the TCPP structure diagram, (b) is the coordination structure diagram, and (c) and (d) are two-dimensional diagrams in two directions.
[0022] Figure 2 FTIR results of the Yb-TCPP metal organic framework compound in Example 1;
[0023] Figure 3 is the TG curve of the Yb-TCPP metal organic framework compound in Example 1;
[0024] Figure 4 The near infrared emission spectrum and the excited singlet oxygen spectrum of the Yb-TCPP metal organic framework compound in Example 1;
[0025] Figure 5 1 is the fluorescence excitation spectrum and fluorescence emission spectrum of the Yb-TCPP metal organic framework compound in Example 1.
[0026] The technical solution of the present invention is further described below in conjunction with embodiments. DETAILED DESCRIPTION
[0027] In the present invention: MOF refers to metal organic framework, and DMF refers to N,N-dimethylacetamide.
[0028] It should be noted that all raw materials used in the present invention, unless otherwise specified, are raw materials known in the art. For example, 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin (TCPP) is a compound known in the prior art, and its CAS code is 14609-54-2.
[0029] In accordance with the above technical scheme, specific embodiments of the present invention are given below. It should be noted that the present invention is not limited to the following specific embodiments, and all equivalent changes made on the basis of the technical scheme of this application fall within the protection scope of the present invention.
[0030] Embodiment 1:
[0031] This embodiment provides a method for preparing a Yb-TCPP metal organic framework compound, which specifically includes the following processes: 9.88 mg of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin (molecular weight 790.79 / 0.0125 mmol) is dissolved in 6.67 mL of N,N-dimethylacetamide to obtain a solution of a compound containing a porphyrin group; 9.69 mg of YbCl3·6H2O (molecular weight 387.49 / 0.025 mmol) is dissolved in 3.33 mL of a hydrochloric acid aqueous solution (2.2 mol / L) to obtain a metal precursor solution; the solution of the compound containing a porphyrin group and the metal precursor solution are transferred to a reactor with a volume of 25 mL, and stirred for 10 minutes with an electromagnetic stirrer; the reactor is placed in an oven, heated to 120°C, kept warm for 72 hours, and then cooled to 30°C at a rate of 5°C / h. In this embodiment, based on the relative molecular mass of DMF being 87.12 and the density being 0.937 g / mL, the amount of DMF is approximately 71.73 mmol, and the molar ratio of hydrochloric acid to DMF is approximately 7.33:71.73.
[0032] After the reaction was completed, the reactor was taken out and purple crystals were seen after opening. The crystals were collected and washed and dried with N,N-dimethylacetamide to obtain crystals with a chemical formula of Yb(TCPP)(DMF)3(H2O) (i.e., Yb-TCPP metal organic framework compound). The above product was characterized and identified, and the results are shown in Table 1. Figure 1 and Figure 2 Based on the above characterization results, it can be determined that the target product has been synthesized.
[0033] Table 1. Crystal data of the Yb-TCPP metal organic framework compound of Example 1
[0034]
[0035] In this embodiment, the yield of the Yb-TCPP metal organic framework compound is 64.1%, and its crystal structure is shown in Figure 1The crystal belongs to the monoclinic system and the space group is P121 / c1. 3+ Coordination Figure 1 a), the carboxyl groups of the porphyrin monomers are coordinated in three different ways. One carboxyl group (denoted as carboxyl group 1) bridges two Yb 3+ ion; another carboxyl group (denoted as carboxyl 2) and Yb 3+ Chelate coordination; the third carboxyl group (denoted as carboxyl 3) has only one O and Yb 3+ The fourth carboxyl group (denoted as carboxyl 4) is protonated and does not participate in coordination. The crystal is a binuclear structure. Coordination environment diagram ( Figure 1 b) shows that the crystal contains only one type of Yb 3+ , Yb 3+ It is seven-coordinated, with 2 O atoms coming from two bridging carboxyl groups 1, 2 O atoms coming from one carboxyl group 2, 1 O atoms coming from one carboxyl group 3, 1 O atoms coming from a water molecule, and 1 O atoms coming from a DMF molecule. In this coordination environment, the longest Yb-O bond length is The shortest Yb-O bond length is The two-dimensional graph is a grid structure ( Figure 1 c), the three carboxyl groups in the porphyrin on the bc plane and Yb 3+ Connected into a two-dimensional plane structure. The two-dimensional structure on the ac plane ( Figure 1 d) Show two Yb 3+ The structural units are connected through the carboxyl groups of porphyrin. The carboxyl group of a porphyrin unit is not connected to a layer of Yb in Figure c. 3+ coordination, but one of the carboxyl groups is connected to the Yb 3+ Staggered coordination forms a MOF material with a three-dimensional structure.
[0036] Analysis of the physicochemical properties of Example 1:
[0037] Figure 3 The thermogravimetric curve of Yb-TCPP metal organic framework compound is shown in Figure 2. Figure 3 It can be seen that when the temperature is between 25 and 300°C, the Yb-TCPP metal organic framework compound slowly loses weight, with a total weight loss of about 13%, which is the weight loss of the solvent molecules DMF and H2O in the Yb-TCPP metal organic framework compound; when the temperature continues to rise to about 500°C, the organic metal framework begins to decompose. Thermogravimetric analysis proves that the Yb-TCPP metal organic framework compound is very stable.
[0038] Embodiment 2:
[0039] This example shows the application of the Yb-TCPP metal organic framework compound prepared in Example 1 for sensitizing singlet oxygen generation. The application specifically includes the following process: 1 mg of the Yb-TCPP metal organic framework compound is added to 1 mL of deuterated chloroform and soaked for 48 hours to allow part of the solvent in the MOF to exchange with the deuterated solvent. The Yb-TCPP metal organic framework compound is then filtered out and dried, and the near-infrared emission spectrum of the material is tested using an FLS920 steady-state transient fluorescence spectrometer. The test results are as follows: Figure 4 , Figure 5 And as shown in Table 2.
[0040] Table 2. Near-infrared luminescence lifetime and fluorescence lifetime of Yb-TCPP metal organic framework compounds
[0041]
[0042] It can be seen from Table 2 that the luminescence lifetime of the Yb-TCPP metal organic framework compound in the near infrared can reach 10 -12 s level, and the fluorescence lifetime can reach 10 -9 s level, indicating that it has excellent luminescence properties. Figure 4 It can be seen that the peak near the wavelength of 980nm is the porphyrin antenna molecule sensitized Yb 3+ The near-infrared luminescence with a peak around 1300nm is the transition emission from singlet oxygen to the ground state, which represents the generation of singlet oxygen sensitized by the porphyrin antenna molecule. Figure 5 It can be seen that the maximum excitation wavelength is 480nm and the maximum emission wavelength is 680nm. This spectrum shows that the energy transfer from the porphyrin triplet state to the rare earth and ground state oxygen in the Yb-TCPP metal organic framework compound is insufficient, so there is still fluorescence emission.
[0043] Comparative Example 1 (different solvents):
[0044] This comparative example provides a method for preparing a Yb-TCPP metal organic framework compound, which is basically the same as Example 1, except that in this comparative example, the solvent used is a DMF solution of HCl in the same molar amount.
[0045] In this comparative example, the Yb-TCPP metal organic framework compound could not be prepared because the structure of the Yb-TCPP metal organic framework compound requires the participation of H2O molecules, and the absence of H2O molecules results in the inability to generate MOF crystals.
[0046] Comparative Example 2 (the ratio of DMF and aqueous hydrochloric acid solution is different):
[0047] This comparative example provides a method for preparing a Yb-TCPP metal organic framework compound, which is basically the same as Example 1, except that in this example, the volume ratio of DMF to the hydrochloric acid aqueous solution is 1 / 2, and the molar ratio of hydrochloric acid to DMF is approximately 29.32:71.73.
[0048] In this comparative example, the Yb-TCPP metal organic framework compound could not be prepared because the change in the ratio of N,N-dimethylacetamide and the hydrochloric acid aqueous solution resulted in the change of the solvent environment and the change of the pH value.
[0049] Comparative Example 3 (different reaction temperatures):
[0050] This comparative example provides a method for preparing a Yb-TCPP metal organic framework compound, which is basically the same as Example 1, except that in this comparative example, the reaction temperature is 150°C.
[0051] In this comparative example, the Yb-TCPP metal organic framework compound could not be prepared because the temperature was too high, the solubility of the material in the high temperature mixed solvent was too large, and the molecular motion was too violent, so the MOF crystals could not nucleate.
[0052] Comparative Example 4 (different reaction times):
[0053] This comparative example provides a method for preparing a Yb-TCPP metal organic framework compound, which is basically the same as Example 1, except that in this comparative example, the reaction time is 36 hours.
[0054] In this comparative example, the yield of the Yb-TCPP metal organic framework compound was 50.3%. Compared with Example 1, the reason why the final yield in this comparative example was lower was that the reaction time was too short, the nucleation and growth process of the MOF crystals had not yet been completed, and the reaction was stopped prematurely.
[0055] Comparative Example 5 (different cooling rates):
[0056] This comparative example provides a method for preparing a Yb-TCPP metal organic framework compound, which is basically the same as Example 1, except that in this comparative example, the cooling rate is 20° C. / min.
[0057] Compared with Example 1, the Yb-TCPP metal organic framework compound obtained in this comparative example has small crystal particles and poor crystal structure, which is similar to powder. The reason is that the cooling rate is too fast, the MOF crystals do not have sufficient time to form, and the growth rate is too fast, resulting in poor crystal structure.
Claims
1. A method for preparing a Yb-TCPP metal organic framework compound, characterized in that: The method comprises: dissolving 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin in N,N-dimethylacetamide to obtain a solution containing a porphyrin group compound; dissolving an ytterbium salt in a hydrochloric acid aqueous solution to obtain a metal precursor solution; transferring the solution containing the porphyrin group compound and the metal precursor solution to a reaction container, stirring, and then keeping the temperature at 110 to 140°C for 48 to 96 hours, and cooling at a rate of 5 to 10°C / h after heating to obtain a Yb-TCPP metal organic framework compound.
2. The method for preparing the Yb-TCPP metal organic framework compound according to claim 1, characterized in that: The molecular formula of the Yb-TCPP metal organic framework compound is Yb2O 24 H 100 N 14 C 114 , its crystals belong to the monoclinic system, P121 / c1 space group.
3. The method for preparing the Yb-TCPP metal organic framework compound according to claim 1, characterized in that: The heating conditions are as follows: heating temperature is 120° C., heating time is 72 h, and cooling is performed at a rate of 5° C. / h after heating.
4. The method for preparing the Yb-TCPP metal organic framework compound according to claim 1, characterized in that: The molar ratio of ytterbium in the 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin and ytterbium salt is 0.0125:0.
025.
5. The method for preparing the Yb-TCPP metal organic framework compound according to claim 1, characterized in that: The concentration of the hydrochloric acid aqueous solution is 2.2 mol / L, and the volume ratio of the hydrochloric acid aqueous solution to N,N-dimethylacetamide is 3.33:6.
67.
6. The method for preparing the Yb-TCPP metal organic framework compound according to claim 1, characterized in that: The ytterbium salt is YbCl3·6H2O.
7. The method for preparing the Yb-TCPP metal organic framework compound according to claim 1, characterized in that: After heating, cool to 20-45°C.
8. The method for preparing the Yb-TCPP metal organic framework compound according to claim 1, characterized in that: The stirring time is 10 to 20 minutes. 9 . A Yb-TCPP metal organic framework compound prepared by the method for preparing a Yb-TCPP metal organic framework compound as claimed in any one of claims 1 to 8 .
10. Use of the Yb-TCPP metal organic framework compound as claimed in claim 9 for sensitizing singlet oxygen generation.