Micro-nano hydrogen bond organic framework as well as preparation method and application thereof

Abstract

The invention discloses a micro-nano hydrogen bond organic framework and a preparation method and application thereof, and belongs to the technical field of micro-nano material preparation. The preparation method of the micro-nano hydrogen bond organic framework comprises the following steps: uniformly mixing an organic ligand and a solvent, and reacting to obtain the micro-nano hydrogen bond organic framework, the organic ligand is a porphyrin or phthalocyanine compound. The preparation method of the micro-nano hydrogen bond organic framework provided by the invention is simple to operate, and the micro-nano hydrogen bond organic framework which is highly crystallized, regular in morphology and uniform in size can be obtained and can be used as an anti-cancer drug carrier, so that the utilization rate of a drug in a living body can be improved.

Description

Technical Field

[0001] The invention belongs to the technical field of micro-nano material preparation, and specifically relates to a micro-nano hydrogen bond organic framework and a preparation method and application thereof. Background Art

[0002] In recent years, ordered porous hydrogen-bonded organic frameworks (HOFs) have attracted increasing attention due to their potential applications in gas adsorption and separation, catalysis, display, sensing, proton conduction, energy storage, and drug loading and delivery. More importantly, compared with metal organic frameworks (MOFs) and covalent organic frameworks (COFs), hydrogen-bonded organic frameworks self-assembled by hydrogen bonds and π-π interactions have lower density, higher solubility, flexible and diverse structures, easy regeneration, good biocompatibility and low toxicity, and can be widely used in the biomedical field.

[0003] Since there are currently few reports on controllable preparation of hydrogen-bonded organic frameworks, the reported materials are large in size and irregular in morphology, and their applications in the biomedical field and other fields are greatly limited. Therefore, the preparation of micro-nano hydrogen-bonded organic frameworks with uniform size and morphology is of great significance for exploring their further applications. Summary of the invention

[0004] The purpose of the present invention is to provide a micro-nano hydrogen-bonded organic framework and its preparation method and application. The micro-nano hydrogen-bonded organic framework can be prepared by using porphyrin or phthalocyanine compounds as organic ligands and adopting a solution method or a solvothermal method.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] One of the technical solutions of the present invention is to provide a method for preparing a micro-nano hydrogen-bonded organic framework, comprising the following steps:

[0007] The organic ligand and the solvent are mixed evenly, and the micro-nano hydrogen bond organic framework is obtained after reaction; the organic ligand is a porphyrin or phthalocyanine compound.

[0008] Preferably, the solvent comprises at least one of water, acetic acid, acetonitrile, ethanol, formic acid, tetrahydrofuran, acetone, dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DEF), N,N-dimethylformamide (DMF) and N-methylpyrrolidone (NMP).

[0009] Preferably, the reaction temperature is 25 to 150° C. and the reaction time is 0.15 to 72 h.

[0010] The reaction temperature of the present invention can be selected to be 25-150° C., that is, both the solution method and the solvent thermal method can be used.

[0011] Preferably, the feedstock further comprises a structure directing agent.

[0012] More preferably, the structure directing agent is an acidic structure directing agent or a basic structure directing agent.

[0013] Particularly preferably, when the structure directing agent is solid, it is first prepared into a solution with a concentration of 1 to 100 mg / mL, and then added at a volume ratio of 0.005 to 1:1 to the solvent; when the structure directing agent is liquid, it is first prepared into a solution with a concentration of 0.1 to 1 mL / mL, and then added at a volume ratio of 0.005 to 1:1 to the solvent.

[0014] Optionally, the acidic structure directing agent includes at least one of hexadecyltrimethylammonium bromide (CTAB), tert-butylamine, tetramethylammonium nitrate, hexamethylenediamine, tetraethylammonium nitrate, ethylenediamine, ethanolamine, hexylamine, hexamethyleneimine, pyridine, imidazole, diethyltriamine, triethylamine, N,N,N',N'-tetramethylenediamine, dimethylamine, piperazine and hexamethylenetetramine; and the alkaline structure directing agent includes at least one of malic acid, maleic acid, oxalic acid, benzoic acid, citric acid, formic acid and acetic acid.

[0015] Preferably, the feedstock also includes a surfactant.

[0016] More preferably, when the surfactant is solid, the ratio of the added amount to the solvent is 0.25-25 mg:1 mL; when the surfactant is liquid, the volume ratio of the added amount to the solvent is 0.005-0.05:1.

[0017] Optionally, the surfactant includes at least one of polyvinyl pyrrolidone (PVP), polyethylene glycol (PEG), polyvinyl alcohol (PVA), sodium dodecylbenzene sulfonate, sodium dodecyl sulfonate, Tween series, Span series, sodium 2-ethylhexyl succinate sulfonate (AOT), Triton X-100 and sodium citrate.

[0018] The present invention selects monomers of porphyrin or phthalocyanine compounds as organic ligands, mixes them with solvents, selects room temperature solution method or solvothermal method, controls reaction time and temperature, and forms a micro-nano hydrogen-bonded organic framework through the synergistic effect of intermolecular hydrogen bond interaction and π-π interaction. Further, a structure directing agent, or a structure directing agent and a surfactant are added to adjust charge balance, fill gaps or act as a template to affect the crystal growth process, thereby obtaining a two-dimensional micro-nano hydrogen-bonded organic framework with a one-dimensional through-hole having a persistent porous structure.

[0019] The second technical solution of the present invention is to provide a micro-nano hydrogen-bonded organic framework prepared according to the preparation method of the micro-nano hydrogen-bonded organic framework.

[0020] The third technical solution of the present invention is to provide an application of the above-mentioned micro-nano hydrogen-bonded organic framework in the preparation of anti-tumor drugs, wherein the micro-nano hydrogen-bonded organic framework serves as a carrier of the anti-tumor drugs.

[0021] The beneficial technical effects of the present invention are as follows:

[0022] The preparation method of the micro-nano hydrogen-bonded organic framework provided by the present invention is simple to operate, and can obtain a micro-nano hydrogen-bonded organic framework with high crystallinity, regular morphology and uniform size, which can be used as an anticancer drug carrier to improve the utilization rate of the drug in vivo. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 The SEM images of the hydrogen-bonded organic framework material based on tetra-p-benzoic acid porphyrin copper in Example 1, wherein (a) and (b) are SEM images at different magnifications.

[0024] Figure 2 This is the PXRD spectrum of the hydrogen-bonded organic framework material based on copper tetraphenylporphyrin in Example 1.

[0025] Figure 3 This is the SEM image of the hydrogen-bonded organic framework material based on cobalt tetraphenylporphyrin in Example 2.

[0026] Figure 4 This is the PXRD spectrum of the hydrogen-bonded organic framework material based on cobalt tetraphenylporphyrin in Example 2.

[0027] Figure 5 This is the SEM image of the hydrogen-bonded organic framework material based on tetra-p-benzoic acid porphyrin manganese in Example 3.

[0028] Figure 6 This is the SEM image of the hydrogen-bonded organic framework material based on tetra-benzoic acid porphyrin iron in Example 4.

[0029] Figure 7 This is an SEM image of the hydrogen-bonded organic framework material based on 1,3,6,8-tetrakis-(4-carboxyphenyl)-pyrene in Method 1 of Example 5.

[0030] Figure 8 This is the PXRD spectrum of the hydrogen-bonded organic framework material based on 1,3,6,8-tetrakis-(4-carboxyphenyl)-pyrene in Example 5 Method 1.

[0031] Fig. 9 This is the SEM image of the hydrogen-bonded organic framework material based on 1,3,6,8-tetrakis-(4-carboxyphenyl)-pyrene in Method 2 of Example 5.

[0032] Fig.10This is the PXRD spectrum of the hydrogen-bonded organic framework material based on 1,3,6,8-tetrakis-(4-carboxyphenyl)-pyrene in Method 2 of Example 5.

[0033] Fig.11 This is the SEM image of the hydrogen-bonded organic framework material based on tetra-benzoic acid porphyrin in Example 6.

[0034] Fig.12 This is the PXRD spectrum of the hydrogen-bonded organic framework material based on tetra-benzoic acid porphyrin in Example 6.

[0035] Fig.13 SEM images of CPT@HOF in the application example, where (a) and (b) are SEM images at different magnifications.

[0036] Fig.14 This is the PXRD pattern of CPT@HOF in the application example.

[0037] Fig.15 The application example is the effect of different concentrations of HOFs on the survival rate of 4T1 cells in in vitro cytotoxicity assay.

[0038] Fig.16 The effect of different concentrations of CPT or CPT@HOF on the survival rate of 4T1 cells in an in vitro cytotoxicity test is shown as an application example.

[0039] Fig.17 Solid images of tumor tissues in mice after 14 days of treatment in different treatment groups in the in vivo evaluation of the application example. DETAILED DESCRIPTION

[0040] Now, various exemplary embodiments of the present invention are described in detail, and this detailed description should not be considered as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, characteristics and embodiments of the present invention. It should be understood that the terms described in the present invention are only for describing specific embodiments and are not used to limit the present invention.

[0041] In addition, for the numerical range in the present invention, it is understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. The intermediate value in any stated value or stated range, and each smaller range between any other stated value or intermediate value in the range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0042] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the invention pertains. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention.

[0043] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0044] Unless otherwise specified, the "room temperature" in the embodiments of the present invention refers to a temperature of 20±10°C.

[0045] Example 1

[0046] Preparation of hydrogen-bonded organic framework materials based on copper tetraphenylporphyrin:

[0047] 0.04 mL of Tween 85 was dispersed in a 5 mL covered glass bottle containing 0.3 mL of DMF and 0.2 mL of NMP. After complete sonication, 2 mg of tetra-p-benzoic acid porphyrin copper (TCPP-Cu) was weighed and added thereto. The ligand was sonicated for about 30 seconds until it was completely dissolved. Then, 2 mL of H2O was added and stirred at room temperature for 5 minutes, followed by 1.6 mL of ethanol and 0.03 mL of citric acid and continued stirring for 30 minutes. After the reaction was completed, the product was centrifuged at 6000 rpm for 2 minutes and washed with ethanol three times to obtain a hydrogen-bonded organic framework material based on tetra-p-benzoic acid porphyrinone.

[0048] The hydrogen-bonded organic framework material based on tetra-benzoic acid porphyrinone was characterized by SEM and PXRD. Figure 1 , where (a) and (b) are SEM images at different magnifications; PXRD patterns are shown in Figure 2 .from Figure 1 It can be seen that by adding acidic structure directing agents and surfactants to adjust charge balance, fill gaps and act as a template to affect the crystal growth process, the tetra-p-benzoic acid porphyrinone-based hydrogen-bonded organic framework material with a uniform nano-block HOF size of 300nm to 500nm is obtained. Figure 2 It can be seen that the PXRD comparison of the hydrogen-bonded organic framework material based on tetra-benzoic acid porphyrinone and the PXRD obtained by computational simulation is Figure 1 The results show that the hydrogen-bonded organic framework material based on tetra-benzoic acid porphyrinone was successfully synthesized.

[0049] Example 2

[0050] Preparation of hydrogen-bonded organic framework materials based on cobalt tetraphenylporphyrin:

[0051] Weigh 1 mg of PVP and disperse it in a 5 mL covered glass bottle containing 1 mL of acetic acid. After it is completely dissolved by ultrasound, weigh 2 mg of tetra-p-benzoic acid porphyrin cobalt (TCPP-Co) and add it. Ultrasonicate for about 30 seconds until the ligand is completely dissolved, then add 0.01 mL of pyridine, shake well, and finally put the resulting uniform solution on a heated magnetic stirrer at 90 ° C and stir evenly at 1400 rpm for 8 hours. After the reaction is completed, the product is centrifuged at 6000 rpm for 2 minutes and washed with ethanol three times in a row to obtain a hydrogen-bonded organic framework material based on tetra-p-benzoic acid porphyrin cobalt.

[0052] The hydrogen-bonded organic framework material based on tetra-benzoic acid porphyrin cobalt was characterized by SEM and PXRD. Figure 3 ; PXRD spectrum see Figure 4 , the scan results are shown in Figure 3 .from Figure 3 It can be seen that the hydrogen-bonded organic framework material based on tetra-p-benzoic acid porphyrin cobalt is a uniform micro-nano strip HOFs with a size of 600nm to 10μm. Figure 4 It can be seen that the hydrogen-bonded organic framework material based on tetra-benzoic acid porphyrin cobalt is compared with the PXRD obtained by computational simulation. Figure 1 It has good crystallinity.

[0053] Example 3

[0054] Preparation of hydrogen-bonded organic framework materials based on tetra-p-benzoic acid porphyrin manganese:

[0055] Weigh 1 mg of PVP and disperse it in a 5 mL covered glass bottle containing 1 mL of acetic acid. After it is completely dissolved by ultrasound, weigh 2 mg of tetra-p-benzoic acid porphyrin manganese (TCPP-Mn) and add it. Ultrasonicate for about 30 seconds until the ligand is completely dissolved, then add 0.01 mL of tetramethylammonium nitrate acetic acid solution (concentration of 10 mg / mL), shake well, and finally put the resulting uniform solution on a heated magnetic stirrer at 90°C and stir evenly at 1400 rpm for 8 hours. After the reaction is completed, the product is centrifuged at 6000 rpm for 2 minutes and washed with ethanol three times to obtain a hydrogen-bonded organic framework material based on tetra-p-benzoic acid porphyrin manganese.

[0056] The hydrogen-bonded organic framework material based on tetra-benzoic acid porphyrin manganese was analyzed by scanning electron microscopy, and the results are shown in Figure 5 .from Figure 5 It can be seen that the hydrogen-bonded organic framework material based on tetra-p-benzoic acid porphyrin manganese is a uniform micro-nano two-dimensional sheet HOFs with a size of 400nm to 10μm.

[0057] Example 4

[0058] Preparation of hydrogen-bonded organic framework materials based on tetra-benzoic acid porphyrin iron:

[0059] Weigh 1 mg of PVP and disperse it in a 5 mL covered glass bottle containing 1 mL of acetic acid. After it is completely dissolved by ultrasound, weigh 2 mg of tetra-p-benzoic acid porphyrin iron (TCPP-Fe) and add it. Ultrasonicate for about 30 seconds until the ligand is completely dissolved, then add 0.01 mL of tetramethylammonium nitrate acetic acid solution (concentration of 10 mg / mL), shake well, and finally put the resulting uniform solution on a heated magnetic stirrer at 90°C and stir evenly at 1400 rpm for 8 hours. After the reaction is completed, the product is centrifuged at 6000 rpm for 2 minutes and washed with ethanol three times to obtain a hydrogen-bonded organic framework material based on tetra-p-benzoic acid porphyrin iron.

[0060] The hydrogen-bonded organic framework material based on tetra-benzoic acid porphyrin iron was analyzed by scanning electron microscopy. Figure 6 .from Figure 6 It can be seen that the hydrogen-bonded organic framework material based on tetra-benzoic acid porphyrin iron is a uniform micro-nano rod-shaped HOFs with a size of 300 nm to 10 μm.

[0061] Example 5

[0062] Preparation of hydrogen-bonded organic framework materials based on 1,3,6,8-tetrakis-(4-carboxyphenyl)-pyrene:

[0063] Method 1:

[0064] Weigh 10 mg of 1,3,6,8-tetrakis-(4-carboxyphenyl)-pyrene and disperse it in a 20 mL covered glass bottle containing 1.5 mL of DMF, dissolve it completely by ultrasonication, add 0.01 mL of CTAB DMF solution (concentration of 10 mg / mL), shake well, then add 10 mL of H2O, put the resulting uniform solution on a heated magnetic stirrer at 25°C and stir evenly at 1400 rpm for 5 minutes, then add 8 mL of ethanol and continue stirring for 10 minutes. After the reaction is completed, centrifuge the product at 6000 rpm for 2 minutes and wash it with ethanol three times to obtain a hydrogen-bonded organic framework material based on 1,3,6,8-tetrakis-(4-carboxyphenyl)-pyrene.

[0065] The hydrogen-bonded organic framework material based on 1,3,6,8-tetrakis-(4-carboxyphenyl)-pyrene was analyzed by scanning electron microscopy. Figure 7 .from Figure 7 It can be seen that the hydrogen-bonded organic framework material based on 1,3,6,8-tetrakis-(4-carboxyphenyl)-pyrene is a uniform micro-nano spherical particle with a size of 500nm to 5μm.

[0066] Method 2:

[0067] Weigh 2 mg of 1,3,6,8-tetrakis-(4-carboxyphenyl)-pyrene and disperse it in a 5 mL covered glass bottle containing 1 mL of formic acid, dissolve it completely by ultrasonication, add 0.01 mL of tetramethylammonium nitrate formic acid solution (concentration of 50 mg / mL), shake well, and finally place the resulting uniform solution on a heated magnetic stirrer at 25°C and stir evenly at 1400 rpm for 30 minutes. After the reaction is completed, the product is centrifuged at 6000 rpm for 2 minutes and washed with ethanol three times in a row to obtain a hydrogen-bonded organic framework material based on 1,3,6,8-tetrakis-(4-carboxyphenyl)-pyrene.

[0068] The hydrogen-bonded organic framework material based on 1,3,6,8-tetrakis-(4-carboxyphenyl)-pyrene was analyzed by scanning electron microscopy. Fig. 9 .from Fig. 9 It can be seen that the hydrogen-bonded organic framework material based on 1,3,6,8-tetrakis-(4-carboxyphenyl)-pyrene is a uniform micro-nano strip particle with a size of 800nm ​​to 5μm.

[0069] For the methods 1 and 2, the hydrogen-bonded organic framework material based on 1,3,6,8-tetrakis-(4-carboxyphenyl)-pyrene was subjected to powder X-ray diffraction analysis. The PXRD pattern of method 1 is shown in Figure 8 The PXRD patterns of method 2 are shown in Fig.10 .from Figure 8 and Fig.10 It can be seen that the hydrogen-bonded organic framework material based on 1,3,6,8-tetrakis-(4-carboxyphenyl)-pyrene is compared with the PXRD obtained by computational simulation. Figure 1 To.

[0070] Example 6

[0071] Preparation of hydrogen-bonded organic framework materials based on tetra-p-benzoic acid porphyrin:

[0072] Weigh 2 mg of tetra-p-benzoic acid porphyrin and disperse it in a 5 mL covered glass bottle filled with a mixed solvent of 0.6 mL acetic acid and 0.4 mL ethanol, completely dissolve it by ultrasonication, and place the resulting uniform solution on a heated magnetic stirrer at 140°C and stir it evenly at 1400 rpm for 5 hours. After the reaction is completed, centrifuge the product at 6000 rpm for 2 minutes and wash it with ethanol three times to obtain a hydrogen-bonded organic framework material based on tetra-p-benzoic acid porphyrin.

[0073] The hydrogen-bonded organic framework material based on tetraphenylporphyrin was analyzed by SEM and powder X-ray diffraction. Fig.11 and Fig.12 .from Fig.11 It can be seen that the size of the hydrogen-bonded organic framework material based on tetra-benzoic acid porphyrin is uniform micro-nano block particles with a size of 500nm to 5μm. Fig.12 It can be seen that the PXRD comparison of the hydrogen-bonded organic framework material based on tetraphenylporphyrin and the computational simulation Figure 1 Good crystallinity.

[0074] Application Examples

[0075] Based on the successful synthesis of the above HOFs, the HOFs material synthesized in Example 1 was selected for biological applications.

[0076] 0.04 mL of Tween 85 was dispersed in a 5 mL covered glass bottle containing 0.3 mL of DMF and 0.2 mL of NMP. After complete sonication, 2 mg of tetra-p-benzoic acid porphyrin copper (TCPP-Cu) and 1 mg of CPT were weighed and added thereto. The ligand was sonicated for about 30 seconds until it was completely dissolved. Then 2 mL of H2O was added and stirred at room temperature for 5 minutes, followed by 1.6 mL of ethanol and 0.03 mL of citric acid and continued stirring for 30 minutes. After the reaction was completed, the product was centrifuged at 6000 rpm for 2 minutes and washed with ethanol for 3 times to obtain a hydrogen-bonded organic framework material loaded with CPT drugs. After the synthesized HOFs material was loaded with camptothecin (CPT) drugs in situ, the HOFs material loaded with camptothecin drugs (CPT@HOF) was characterized by SEM and PXRD. The SEM image of CPT@HOF is shown in Figure 13, where (a) and (b) are SEM images at different magnifications; the PXRD spectrum of CPT@HOF is shown in Figure 13. Fig.14 .from Fig.14 It can be seen that the HOFs framework material loaded with camptothecin drugs is a uniform nano-block HOF with a size of 400nm to 500nm, indicating that the size increases slightly after loading camptothecin drugs, and the morphology is consistent. Fig.14 It can be seen that the PXRD comparison between the HOFs material loaded with camptothecin and the PXRD obtained by computational simulation Figure 1 This indicates that the camptothecin drug is successfully loaded into the HOFs material without affecting the structure of the HOFs material.

[0077] In vitro cytotoxicity tests of HOFs, CPT and CPT@HOF:

[0078] 4T1 cells were seeded in a 96-well plate at a density of 6000 cells per well and cultured in 1640 medium for 24 hours. The original medium was then aspirated and new medium with different concentrations of HOF was added. After the cells were incubated for 24 hours, the culture medium was discarded again and fresh 1640 containing 10 μL MTT was added. After 4 hours in the dark, 150 μL DMSO was added to each well. The survival rate of 4T1 cells was determined using a microplate reader. The results are shown in Fig.15 .from Fig.15It can be seen that the biosafety results of HOFs in 4T1 cells showed that at different concentrations (0-100 μg mL -1 ) of HOFs, most cells survived after 24 h of incubation. -1 When the cells were heated to 4 ℃ and 8 ℃, about 90% of the cells were still alive, indicating that HOFs have good biocompatibility.

[0079] 4T1 cells were seeded in a 96-well plate at a density of 6000 cells per well and cultured in 1640 medium for 24 hours. The original medium was then aspirated and new medium with different concentrations of CPT and CPT@HOF was added. After the cells were incubated for 24 hours, the culture medium was discarded again and fresh 1640 containing 10 μL MTT was added. After 4 hours in the dark, 150 μL DMSO was added to each well. The survival rate of 4T1 cells was determined by a microplate reader. The results are shown in Fig.16 .like Fig.16 As shown in Figure 2, even in the presence of a small amount of CPT or CPT@HOF, cell viability decreased significantly, demonstrating an excellent ability to kill cancer cells. -1 Therefore, in order to minimize the toxic side effects, the optimal concentrations of CPT and CPT@HOF were both 34.8 μg mL -1 .

[0080] In vivo evaluation of the antitumor efficacy of HOFs, CPT, and CPT@HOF:

[0081] The mouse model was established by subcutaneously injecting 4T1 cancer cells into the right leg of female Balb / C mice. 3 At the same time, 20 tumor-bearing mice were randomly divided into 4 groups and given PBS, HOFs, CPT and CPT@HOF (all 5 mg·Kg -1 ) treatment, marked as I, II, III, IV. Each group of mice received two drug injections on the first day and the seventh day, and the tumor tissues of each mouse were removed 14 days later. The results are shown in Fig.17 .like Fig.17 As shown, the average relative tumor volume of the CPT@HOF group was much smaller than that of the other three groups, and even smaller than that of the CPT group, indicating that the anticancer effect of CPT@HOF was enhanced.

[0082] The embodiments described above are only descriptions of the preferred modes of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should all fall within the protection scope determined by the claims of the present invention.

Claims

1. A method for preparing a micro-nano hydrogen-bonded organic framework, characterized in that: The following steps are involved: The organic ligand and the solvent are mixed evenly, and the micro-nano hydrogen bond organic framework is obtained after reaction; the organic ligand is a porphyrin or phthalocyanine compound.

2. The method for preparing a micro-nano hydrogen-bonded organic framework according to claim 1, characterized in that: The solvent includes at least one of water, acetic acid, acetonitrile, ethanol, formic acid, tetrahydrofuran, acetone, dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide and N-methylpyrrolidone.

3. The method for preparing a micro-nano hydrogen-bonded organic framework according to claim 1, characterized in that: The reaction temperature is 25-150° C. and the reaction time is 0.15-72 h.

4. The method for preparing a micro-nano hydrogen-bonded organic framework according to claim 1, characterized in that: The raw materials also include structure directing agents.

5. The method for preparing a micro-nano hydrogen-bonded organic framework according to claim 4, characterized in that: When the structure directing agent is solid, first prepare a solution with a concentration of 1 to 100 mg / mL, and then add it at a volume ratio of 0.005 to 1:1 with the solvent; when the structure directing agent is liquid, first prepare a solution with a concentration of 0.1 to 1 mL / mL, and then add it at a volume ratio of 0.005 to 1:1 with the solvent.

6. The method for preparing a micro-nano hydrogen-bonded organic framework according to claim 5, characterized in that: The raw materials also include surfactants.

7. The method for preparing a micro-nano hydrogen-bonded organic framework according to claim 6, characterized in that: When the surfactant is solid, the ratio of the added amount to the solvent is 0.25-25 mg:1 mL; when the surfactant is liquid, the volume ratio of the added amount to the solvent is 0.005-0.05:

1.

8. The method for preparing a micro-nano hydrogen-bonded organic framework according to claim 6, characterized in that: The surfactant includes at least one of polyvinyl pyrrolidone, polyethylene glycol, polyvinyl alcohol, sodium dodecylbenzene sulfonate, sodium dodecyl sulfonate, Tween series, Span series, sodium 2-ethylhexyl succinate sulfonate, Triton X-100 and sodium citrate.

9. A micro-nano hydrogen-bonded organic framework prepared according to the method for preparing a micro-nano hydrogen-bonded organic framework according to any one of claims 1 to 8.

10. Use of the micro-nano hydrogen-bonded organic framework according to claim 9 in the preparation of anti-tumor drugs, characterized in that: The micro-nano hydrogen-bonded organic framework serves as a carrier of the anti-tumor drug.

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