A host-guest water-soluble metal-organic cage material, its preparation method and application

Abstract

A host-guest water-soluble metal-organic cage material, which is a host-guest coordination polymer presenting a spatial octahedral configuration, has a particle size of 20-100 nm when dispersed in an aqueous solution, and can maintain its original spatial configuration in an aqueous solution system; the structural formula of this material is: The water-soluble property is beneficial to its application in biomedicine. This material has low toxicity to normal cells within a certain concentration range, and has good photothermal conversion efficiency under the irradiation of 808 nm near-infrared light at low concentrations. This material can use Pd<supgt;2+< / supgt; or Pt<supgt;2+< / supgt; as metal nodes. When Pt<supgt;2+< / supgt; ions are present, this material can achieve the synergistic elimination of tumor cells by photothermal therapy and chemotherapy.

Description

(1) Technical Field:

[0001] The present invention relates to the field of organic cage materials, and in particular to a host-guest water-soluble metal-organic cage material, a preparation method thereof, and an application. (2) Background Art:

[0002] The treatment of cancer is one of the current research hotspots. Most of the means for cancer treatment are chemotherapy, radiotherapy, and surgery. However, these methods have certain drawbacks. Photothermal therapy uses a photothermal drug to absorb near-infrared (NIR) light to reach a temperature of 45-50 °C, ablating tumor cells with a poor vascularized microenvironment in the targeted area, and causing irreversible damage to the diseased protein cells in the targeted area by changing gene expression, ultimately achieving a therapeutic effect. At the same time, the relatively low overheating temperature can prevent unnecessary damage to non-targeted areas, so it exhibits characteristics such as a small action range and mild action conditions compared with traditional treatment methods. However, when using a photothermal material to treat cancer, external illumination at 808 nm is required, and the heat generation effect is lost when the illumination is stopped, so it cannot inhibit the growth of tumor cells for a long time.

[0003] Since the discovery of cisplatin, more and more pharmacists have been committed to rationally designing drugs that can treat cancer. It is generally recognized that after cisplatin enters the cell, it will bind to the DNA in the cell to produce a Pt-DNA conjugate, thereby destroying the DNA binding and inhibiting cell reproduction. (3) Summary of the Invention:

[0004] To solve the defect that photothermal materials cannot inhibit the growth of tumor cells for a long time, the present invention provides a preparation method and an application of a host-guest water-soluble metal-organic cage material. The present invention is a host-guest water-soluble metal-organic cage material, which can produce a "thermal killing" effect under the irradiation of an 808 nm near-infrared laser. When the illumination is removed, the material with Pt 2+ as the metal node can act as a chemotherapeutic drug to continue to inhibit the growth of tumor cells.

[0005] The technical solution of the present invention is: A host-guest water-soluble metal-organic cage material, which is a host-guest coordination polymer presenting a spatial octahedral configuration, has a particle size of 20-100 nm when dispersed in an aqueous solution, and can maintain its original spatial configuration in an aqueous solution system; the structural formula of this material is: wherein, M = Pd 2+ , Pt 2+ , X = cis-1,2-Diaminocyclohexane, 2,2-Dipyridyl, and different metal ions and different encapsulation ends are selected to obtain wherein, in 1a, M = Pd2+ , X = cis-1,2-Diaminocyclohexane, M = Pt in 1b 2+ , X = cis-1,2-Diaminocyclohexane, M = Pd in 2a 2+ , X = 2,2-Dipyridyl, M = Pd in 2b 2+ , X = 2,2-Dipyridyl.

[0006] The host-guest water-soluble metal-organic cage biomaterial is prepared from a precursor complex, pyridinetriazine (TPT), and tetrathiafulvalene (TTF); the precursor complex is one of palladium nitrate 1,2-diaminocyclohexane, platinum nitrate 1,2-diaminocyclohexane, palladium nitrate 2,2-bipyridine, and platinum nitrate 2,2-bipyridine.

[0007] The raw materials for synthesizing the precursor complex include palladium chloride (PdCl2), potassium chloroplatinate (K2PtCl4), 1,2-diaminocyclohexane, 2,2-bipyridine, silver nitrate (AgNO3), deionized water (H2O), methanol (MeOH), hydrochloric acid (HCl), and nitric acid (HNO3).

[0008] A preparation method of a host-guest water-soluble metal-organic cage material comprises the following steps:

[0009] (1) Synthesize the precursor complex;

[0010] (2) Self-assemble the precursor complex obtained in step (1) with pyridinetriazine (TPT) in an aqueous solution or a methanol-aqueous solution to form a water-soluble metal-organic cage with an octahedral configuration in space, filter the unreacted components, and obtain cage powder by freeze-drying;

[0011] (3) Mix the cage powder obtained in step (2) with tetrathiafulvalene (TTF) in an aqueous solution and stir at room temperature under dark conditions to obtain the host-guest water-soluble metal-organic cage material.

[0012] The precursor complex is one of palladium nitrate 1,2-diaminocyclohexane, platinum nitrate 1,2-diaminocyclohexane, palladium nitrate 2,2-bipyridine, and platinum nitrate 2,2-bipyridine;

[0013] Among them, the synthesis of palladium nitrate 1,2-cyclohexanediamine: Dissolve 2 mmol of 1,2-cyclohexanediamine, 2 mmol of palladium chloride, and 4 mmol of potassium chloride in 10 - 15 mL of aqueous solution, stir at 70 °C for 4 - 6 h to obtain a yellow solution. Add 0.85 mL of 5 mol / L concentrated hydrochloric acid, stir at room temperature to obtain a yellow precipitate, then filter and dry; Dissolve the obtained yellow precipitate and 4 mmol of silver nitrate in 10 - 15 mL of water, and add dropwise 80 - 100 μL of 5 mol / L nitric acid, stir at 100 °C in the dark for 4 - 6 h, filter off the white precipitate, and rotary evaporate and dry the obtained yellow solution to obtain a yellow product, which is palladium nitrate 1,2-cyclohexanediamine;

[0014] The synthesis of platinum nitrate 1,2-cyclohexanediamine: Dissolve 2 mmol of 1,2-cyclohexanediamine and 2 mmol of potassium chloroplatinate in 15 mL of aqueous solution, add 250 - 300 μL of 5 mol / L hydrochloric acid, stir at 70 °C for 4 - 6 h to obtain a yellow precipitate, then filter and dry; Dissolve the obtained yellow precipitate and 4 mmol of silver nitrate in 10 mL of water, and add dropwise 80 - 100 μL of 5 mol / L nitric acid, stir overnight at 100 °C in the dark, filter off the white precipitate, and rotary evaporate and dry the obtained yellow solution to obtain a yellow product, which is platinum nitrate 1,2-cyclohexanediamine;

[0015] The synthesis of palladium nitrate 2,2'-bipyridine: Dissolve 0.5 mmol of 2,2'-bipyridine and 0.5 mmol of palladium chloride in 15 mL of aqueous solution, add 250 - 300 μL of 5 mol / L hydrochloric acid, stir at 70 °C for 4 - 6 h to obtain a yellow precipitate, then filter and dry; Dissolve the obtained yellow precipitate and 1 mmol of silver nitrate in 15 mL of water, and add dropwise 80 - 100 μL of 5 mol / L nitric acid, stir overnight at 100 °C in the dark, filter off the white precipitate, and rotary evaporate and dry the obtained yellow solution to obtain a yellow product, which is palladium nitrate 2,2'-bipyridine;

[0016] The synthesis of platinum nitrate 2,2'-bipyridine: Dissolve 0.5 mmol of 2,2'-bipyridine and 0.5 mmol of potassium chloroplatinate in 15 mL of aqueous solution, add 250 - 300 μL of 5 mol / L hydrochloric acid, stir at 70 °C for 4 - 6 h to obtain a yellow precipitate, then filter and dry; Dissolve the obtained yellow precipitate and 1 mmol of silver nitrate in 15 mL of water, and add dropwise 80 - 100 μL of 5 mol / L nitric acid, stir overnight at 100 °C in the dark, filter off the white precipitate, and rotary evaporate and dry the obtained yellow solution to obtain a yellow product, which is platinum nitrate 2,2'-bipyridine.

[0017] The host-guest water-soluble metal-organic cage material is or

[0018] Among them, The synthesis method of is as follows: First, weigh 12 μmol of the precursor complex 1,2-cyclohexanediamine palladium nitrate and 8 μmol of TPT, stir them in 1 mL of distilled water at 100 °C for 1 h, filter the remaining product while it is hot, and freeze-dry the obtained solution to obtain a pale yellow powder; then weigh 2 μmol of cage powder and 4 mg of TTF, stir them in 1 mL of distilled water at 60 °C for 6 h to obtain a solution;

[0019] The The synthesis method of is as follows: First, weigh 12 μmol of the precursor complex 1,2-cyclohexanediamine platinum nitrate and 8 μmol of TPT, stir them in 1 mL of distilled water at 100 °C for 1 h, filter the remaining product, and freeze-dry the obtained solution to obtain a pale yellow powder; then weigh 2 μmol of cage powder and 4 mg of TTF, stir them in 1 mL of distilled water at 60 °C for 6 h to obtain a solution;

[0020] The The synthesis method of is as follows: First, weigh 12 μmol of the precursor complex 2,2-bipyridine palladium nitrate and 8 μmol of TPT, stir them in a 1 mL mixed solution of water and methanol (4:1) at 100 °C for 30 min, filter the remaining product, and freeze-dry the obtained solution to obtain a pale yellow powder; then weigh 2 μmol of cage powder and 4 mg of TTF, stir them in 1 mL of distilled water at room temperature for 4 h to obtain a solution;

[0021] The The synthesis method of is as follows: First, weigh 12 μmol of the precursor complex 2,2-bipyridine platinum nitrate and 8 μmol of TPT, stir them in a 1 mL mixed solution of water and methanol (4:1) at 100 °C for 4 h, filter the remaining product, and freeze-dry the obtained solution to obtain a pale yellow powder; then weigh 2 μmol of cage powder and 4 mg of TTF, stir them in 1 mL of distilled water at room temperature overnight to obtain a solution.

[0022] The host-guest water-soluble metal-organic cage material is applied to photothermal conversion. It has a high photothermal conversion efficiency under the irradiation of an 808 nm near-infrared laser, and the extreme value of the material temperature rise can be controlled at different power densities and different concentrations.

[0023] The light source used in the photothermal conversion test is an 808 nm near-infrared laser, and different power densities (1 w / cm 2 、1.5 w / cm 2 、2 w / cm2 ) and host-guest water-soluble metal organic cages with different concentrations (1μmol / mL, 2μmol / mL, 4μmol / mL) were tested for photothermal conversion.

[0024] Any host-guest water-soluble metal organic cage material can be used with a solution concentration of 2 μmol / mL at a power density of 0.75 w / cm 2 、1w / cm 2 、1.5w / cm 2 The wavelength of the laser is 808nm and the apoptosis temperature reaches above 50℃.

[0025] The host-guest water-soluble metal organic cage material is used in chemotherapy. The prepared material was diluted according to a certain concentration gradient and added to a culture dish of mouse fibroblasts (L929). After incubation with the cells for 48 hours, the survival rate of normal cells reached more than 80%, indicating that the material has good cell compatibility. 2+ The material containing Pt was co-incubated with mouse breast cancer cells (4T1) whose intracellular fluid was acidic, and a lower survival rate was obtained compared with normal cells, indicating that the Pt 2+ The ionic material can play a good chemotherapy effect. On this basis, applying 808nm near-infrared light to the co-incubated material further reduced the survival rate of mouse breast cancer cells.

[0026] A host-guest water-soluble metal organic cage material is selected, which has low toxicity to normal cells at a concentration of 50-100 μM. The metal node is Pt 2+ The ionic host-guest metal-organic cage has a higher lethality rate in mouse breast cancer cells at an acidic pH. Furthermore, under 808nm near-infrared laser irradiation, the survival rate of mouse breast cancer cells continues to decrease.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] (1) A simple one-pot method can be used to obtain host-guest water-soluble metal organic cages, which maintain a spatial octahedral structure when dispersed in aqueous solution. The particle size is 20 to 50 nm. Its water-soluble properties lay a certain foundation for its application in the biological field.

[0029] (2) The present invention has a more obvious response to 808nm near-infrared laser, has a higher photothermal conversion efficiency, and can play a role in photothermal treatment. 2+ The host-guest water-soluble metal-organic cages as metal nodes not only have the properties of photothermal conversion, but can also play a chemotherapeutic role as chemical drugs.

[0030] (3) The present invention can utilize the different pH values of the internal environments of normal cells and tumor cells to produce different degrees of chemotherapeutic effects. For Pt 2+ The host-guest water-soluble metal-organic cage as a metal node has low biotoxicity and high biocompatibility at low concentrations. And it shows a higher killing effect in tumor cells with a lower pH. (IV) Description of the Drawings:

[0031] Figure 1 Schematic diagram of the host-guest water-soluble metal-organic cage prepared in Example 1.

[0032] Figure 2 NMR spectrum of the water-soluble metal-organic cage prepared with 1,2-cyclohexanediamine palladium nitrate as the precursor complex in Example 1.

[0033] Figure 3 NMR spectrum of the water-soluble metal-organic cage prepared with 2,2'-bipyridine palladium nitrate as the precursor complex in Example 1.

[0034] Figure 4 Mass spectrum of the water-soluble metal-organic cage prepared with 1,2-cyclohexanediamine palladium nitrate as the precursor complex in Example 1.

[0035] Figure 5 Mass spectrum of the water-soluble metal-organic cage prepared with 2,2'-bipyridine platinum nitrate as the precursor complex in Example 1.

[0036] Figure 6 Particle size test chart of the host-guest water-soluble metal-organic cage in Example 2.

[0037] Figure 7 For Example 3 Result data chart of the photothermal conversion test.

[0038] Figure 8 For Example 4 Results of the biocompatibility test.

[0039] Figure 9 For Example 4 and Biocompatibility test at low concentrations.

[0040] Figure 10 For Example 5 Test results of cell viability after co-incubation with 4T1 cells and increasing 808 nm near-infrared light irradiation at low concentrations. (V) Specific Embodiments:

[0041] The present invention will be further described below in conjunction with specific embodiments.

[0042] Example 1: (1) Synthesis of precursors:

[0043] Synthesis of palladium nitrate of 1,2 - cyclohexanediamine: Dissolve 2 mmol of 1,2 - cyclohexanediamine, 2 mmol of palladium chloride, and 4 mmol of potassium chloride in 10 - 15 mL of aqueous solution, stir at 70 °C for 4 hours to obtain a yellow solution. Add 0.85 mL of 5 mol / L concentrated hydrochloric acid, stir at room temperature to obtain a yellow precipitate, then filter and dry. Dissolve the obtained yellow precipitate and 4 mmol of silver nitrate in 10 - 15 mL of water, and add 100 μL of 5 mol / L nitric acid dropwise. Stir at 100 °C in the dark for 4 h, filter off the white precipitate, and rotary evaporate and dry the obtained yellow solution to obtain a yellow product, which is the precursor palladium nitrate of 1,2 - cyclohexanediamine;

[0044] Synthesis of platinum nitrate of 1,2 - cyclohexanediamine: Dissolve 2 mmol of 1,2 - cyclohexanediamine and 2 mmol of potassium chloroplatinate in 15 mL of aqueous solution, add 300 μL of 5 mol / L hydrochloric acid, stir at 70 °C for 4 hours to obtain a yellow precipitate, then filter and dry. Dissolve the obtained yellow precipitate and 4 mmol of silver nitrate in 10 mL of water, and add 100 μL of 5 mol / L nitric acid dropwise. Stir at 100 °C in the dark overnight, filter off the white precipitate, and rotary evaporate and dry the obtained yellow solution to obtain a yellow product, which is the precursor platinum nitrate of 1,2 - cyclohexanediamine;

[0045] Synthesis of palladium nitrate of 2,2 - bipyridine: Dissolve 0.5 mmol of 2,2 - bipyridine and 0.5 mmol of palladium chloride in 15 ml of aqueous solution, add 300 μL of 5 mol / L hydrochloric acid, stir at 70 °C for 4 hours to obtain a yellow precipitate, then filter and dry. Dissolve the obtained yellow precipitate and 1 mmol of silver nitrate in 15 mL of water, and add 100 μL of 5 mol / L nitric acid dropwise. Stir at 100 °C in the dark overnight, filter off the white precipitate, and rotary evaporate and dry the obtained yellow solution to obtain a yellow product, which is the precursor palladium nitrate of 2,2 - bipyridine;

[0046] Synthesis of platinum nitrate of 2,2 - bipyridine: Dissolve 0.5 mmol of 2,2 - bipyridine and 0.5 mmol of potassium chloroplatinate in 15 ml of aqueous solution, add 300 μL of 5 mol / L hydrochloric acid, stir at 70 °C for 4 hours to obtain a yellow precipitate, then filter and dry. Dissolve the obtained yellow precipitate and 1 mmol of silver nitrate in 15 mL of water, and add 100 μL of 5 mol / L nitric acid dropwise. Stir at 100 °C in the dark overnight, filter off the white precipitate, and rotary evaporate and dry the obtained yellow solution to obtain a yellow product, which is the precursor platinum nitrate of 2,2 - bipyridine.

[0047] (2) Optionally, take 12 μmol of a precursor obtained in step (1) and 8 μmol of TPT, heat and stir in an aqueous (water - methanol) solution, filter off the undissolved components to obtain a water - soluble metal - organic cage with a spatial octahedral configuration; freeze - dry the resulting light - yellow solution to obtain cage powder.

[0048] Among them, the synthesis method of the first kind of cage powder: First, weigh 12 μmol of the precursor complex 1,2 - cyclohexanediamine palladium nitrate and 8 μmol of TPT, stir at 100 °C in 1 mL of distilled water for 1 h, filter the remaining product while it is hot, and freeze - dry the resulting solution to obtain a light - yellow powder, which is the first kind of cage powder;

[0049] The synthesis method of the second kind of cage powder: First, weigh 12 μmol of the precursor complex 1,2 - cyclohexanediamine platinum nitrate and 8 μmol of TPT, stir at 100 °C in 1 mL of distilled water for 1 h, filter the remaining product, and freeze - dry the resulting solution to obtain a light - yellow powder, which is the second kind of cage powder;

[0050] The synthesis method of the third kind of cage powder: First, weigh 12 μmol of the precursor complex 2,2 - bipyridine palladium nitrate and 8 μmol of TPT, stir at 100 °C in a 1 mL mixed solution of water and methanol (4∶1) for 30 min, filter the remaining product, and freeze - dry the resulting solution to obtain a light - yellow powder, which is the third kind of cage powder;

[0051] The synthesis method of the fourth kind of cage powder: First, weigh 12 μmol of the precursor complex 2,2 - bipyridine platinum nitrate and 8 μmol of TPT, stir at 100 °C in a 1 mL mixed solution of water and methanol (4∶1) for 4 h, filter the remaining product, and freeze - dry the resulting solution to obtain a light - yellow powder, which is the fourth kind of cage powder.

[0052] Example 2: Mix 4 mg of TTF with 2 μmol of cage powder and stir at room temperature for 4 - 8 h in the dark in an aqueous solution to obtain a host - guest water - soluble metal - organic cage;

[0053] (1) Weigh 2 μmol of the first kind of cage powder and 4 mg of TTF, stir at 60 °C in 1 mL of distilled water for 6 h to obtain a 2 μmol / mL solution of the first kind of host - guest water - soluble metal - organic cage solution;

[0054] (2) Weigh 2 μmol of the second kind of cage powder and 4 mg of TTF, stir at 60 °C in 1 mL of distilled water for 6 h to obtain a 2 μmol / mL solution of the second kind of host - guest water - soluble metal - organic cage solution;

[0055] (3) Weigh 2 μmol of cage powder and 4 mg of TTF, stir them in 1 mL of distilled water at room temperature for 4 h to obtain a third host-guest water-soluble metal-organic cage solution;

[0056] (4) Weigh 2 μmol of cage powder and 4 mg of TTF, stir them in 1 mL of distilled water at room temperature overnight to obtain a fourth host-guest water-soluble metal-organic cage solution.

[0057] Example 3:

[0058] Add 0.5 mL of the obtained host-guest water-soluble organic cage solution into 3-mL centrifuge tubes respectively. Place the 808 nm laser head vertically close to the top of the centrifuge tube. Irradiate the solutions with light beams of six power densities of 0.25 w / cm 2 , 0.5 w / cm 2 , 0.75 w / cm 2 , 1 w / cm 2 , 1.25 w / cm 2 , 1.5 w / cm 2 respectively. Use a temperature detector to record the temperature every 10 s until 300 s. Stop irradiating when one of the power densities reaches the highest temperature, record the time it takes to return to room temperature, and calculate its photothermal conversion efficiency. Conduct a thermal cycling test on the obtained material. After irradiating to the highest temperature and stopping irradiation until it returns to room temperature, continue to irradiate the solution for several cycles. The experimental data show that the photothermal conversion efficiency of this material is 40.06% and it has good stability and recyclability, and can be used repeatedly.

[0059] Example 4:

[0060] Add the 2 μmol / mL host-guest water-soluble organic cage solution into 1 mL of culture medium containing L929 in different volumes to dilute its concentration. After 48 h, take the supernatant to obtain the survival rate after co-incubation with L929. By comparison, it is found that the material with Pd2+ as the metal node has low toxicity at a concentration of 125 μM, and the cell survival rate is close to 100%. Compared with the material with Pt2+ as the metal node, when the concentration is 50 μM, the cell survival rate can be close to 100%. This is because Pt can act as a chemical drug to achieve the effect of chemotherapy.

[0061] Example 5:

[0062] Add the 2 μmol / mL host-guest water-soluble organic cage solution into 1 mL of culture medium containing 4T1 in different volumes, make two groups of controls. After 48 h, take the supernatant to obtain the survival rate of 4T1. Then, irradiate the control group with 808 nm light, using 4 w / cm2 After irradiating for 5 min, the supernatant was removed to obtain the survival rate after irradiation. When the material concentration with Pt as the metal node material was 50 μM, the survival rate of normal cells was close to 100%. However, in tumor cells with a slightly acidic environment, the lethality was increased, and the survival rate of tumor cells decreased. After applying 808 nm near-infrared laser irradiation, the cell survival rate further decreased, indicating that this material can achieve the synergistic elimination of tumor cells by photothermal-chemical therapy.

Claims

1. A host-guest water-soluble metal-organic cage material, characterized in that Its structural formula is: [M6X6(TPT)4]·(NO3) 12 @(TTF) 1~4 , where M = Pd 2+ , Pt 2+ ,X=cis-1,2-Diaminocyclohexane,2,2-Dipyridyl,select different metal ions and different encapsulation ends to obtain 1a@(TTF) 1~4 、1b@(TTF) 1~4 、2a@(TTF) 1~4 、2b@(TTF) 1~4 , where M=Pd in 1a 2+ , X=cis-1,2-Diaminocyclohexane, 1b in which M=Pt 2+ , X=cis-1,2-Diaminocyclohexane, M=Pd in 2a 2+ ,X=2,2-Dipyridyl,M=Pt in 2b 2+ , X=2,2-Dipyridyl; the cis-1,2-Diaminocyclohexane is cis-1,2-cyclohexanediamine; the 2,2-Dipyridyl is 2,2-bipyridine; the TPT is pyridinetriazine; and the TTF is tetrathiafulvalene.

2. The host-guest water-soluble metal-organic cage material according to claim 1, wherein It is a host-guest coordination polymer presenting a spatial octahedral configuration, with a particle size of 20-100 nm when dispersed in an aqueous solution, and capable of maintaining the original spatial configuration in an aqueous solution system.

3. The host-guest water-soluble metal-organic cage material according to claim 2, wherein It is prepared from a precursor complex, pyridinetriazine, and tetrathiafulvalene; the precursor complex is one of cis-1,2-cyclohexanediamine palladium nitrate, cis-1,2-cyclohexanediamine platinum nitrate, 2,2-bipyridine palladium nitrate, and 2,2-bipyridine platinum nitrate; the raw materials for synthesizing the precursor complex include palladium chloride, potassium chloroplatinate, cis-1,2-cyclohexanediamine, 2,2-bipyridine, silver nitrate, deionized water, methanol, hydrochloric acid, and nitric acid.

4. A method for preparing the host-guest water-soluble metal-organic cage material according to claim 1, characterized in that It includes the following steps: (1) Synthesize the precursor complex; (2) Self-assemble the precursor complex obtained in step (1) with pyridinetriazine in an aqueous solution or a methanol-aqueous solution to form a water-soluble metal-organic cage with a spatial octahedral configuration, filter the unreacted components, and obtain the cage powder by freeze-drying; (3) Mix the cage powder obtained in step (2) with tetrathiafulvalene in an aqueous solution and stir at room temperature under dark conditions to obtain the host-guest water-soluble metal-organic cage material; The synthesis method of the precursor complex in step (1) is as follows: Dissolve one of palladium chloride or potassium chloroplatinate and one of cis-1,2-cyclohexanediamine or 2,2-bipyridine in an aqueous solution, add hydrochloric acid, stir, filter and dry after obtaining a yellow precipitate; Dissolve the obtained yellow precipitate and silver nitrate in water, add nitric acid dropwise, stir, filter off the white precipitate, and rotary evaporate and dry the obtained yellow solution to obtain the precursor complex.

5. The preparation method of a host-guest water-soluble metal-organic cage material according to claim 4, wherein The precursor complex is one of cis-1,2-cyclohexanediamine palladium nitrate, cis-1,2-cyclohexanediamine platinum nitrate, 2,2-bipyridine palladium nitrate, and 2,2-bipyridine platinum nitrate; Among them, the synthesis of cis-1,2-cyclohexanediamine palladium nitrate: Dissolve cis-1,2-cyclohexanediamine, palladium chloride, and potassium chloride in an aqueous solution and stir to obtain a yellow solution, add hydrochloric acid, stir at room temperature to obtain a yellow precipitate, then filter and dry; Dissolve the obtained yellow precipitate and silver nitrate in water, add nitric acid dropwise, stir, filter off the white precipitate, and rotary evaporate and dry the obtained yellow solution to obtain a yellow product, which is cis-1,2-cyclohexanediamine palladium nitrate; The synthesis of cis-1,2-cyclohexanediamine platinum nitrate: Dissolve cis-1,2-cyclohexanediamine and potassium chloroplatinate in an aqueous solution, add hydrochloric acid, stir, filter and dry after obtaining a yellow precipitate; Dissolve the obtained yellow precipitate and silver nitrate in water, add nitric acid dropwise, stir, filter off the white precipitate, and rotary evaporate and dry the obtained yellow solution to obtain a yellow product, which is cis-1,2-cyclohexanediamine platinum nitrate; Synthesis of palladium(II) 2,2'-bipyridine dinitrate: Dissolve 2,2'-bipyridine and palladium(II) chloride in an aqueous solution, add hydrochloric acid, stir, filter and dry after obtaining a yellow precipitate; Dissolve the obtained yellow precipitate and silver nitrate in water, add nitric acid dropwise, stir, filter off the white precipitate, and rotary evaporate and dry the obtained yellow solution to obtain a yellow product, which is palladium(II) 2,2'-bipyridine dinitrate; Synthesis of platinum(II) 2,2'-bipyridine dinitrate: Dissolve 2,2'-bipyridine and potassium chloroplatinate in an aqueous solution, add hydrochloric acid, stir, filter and dry after obtaining a yellow precipitate; Dissolve the obtained yellow precipitate and silver nitrate in water, add nitric acid dropwise, stir, filter off the white precipitate, and rotary evaporate and dry the obtained yellow solution to obtain a yellow product, which is platinum(II) 2,2'-bipyridine dinitrate.

6. The preparation method of a host-guest water-soluble metal-organic cage material according to claim 4, characterized in that The synthesis method of the 1a@(TTF) 1~4 is as follows: First, weigh 12 μmol of the precursor complex cis-1,2-cyclohexanediamine palladium nitrate and 8 μmol of TPT, stir them in 1 mL of distilled water at 100 °C for 1 h, filter the remaining product while it is hot, and freeze-dry the obtained solution to get a pale yellow powder; then weigh 2 μmol of cage powder and 4 mg of TTF, stir them in 1 mL of distilled water at 60 °C for 6 h to obtain a 2 μmol / mL 1a@(TTF) 1~4 solution; The synthesis method of 1b@(TTF) 1~4 is as follows: First, weigh 12 μmol of the precursor complex cis-1,2-cyclohexanediamine platinum nitrate and 8 μmol of TPT, stir them in 1 mL of distilled water at 100 °C for 1 h, filter the remaining product, and freeze-dry the obtained solution to get a pale yellow powder; then weigh 2 μmol of cage powder and 4 mg of TTF, stir them in 1 mL of distilled water at 60 °C for 6 h to obtain a 2 μmol / mL solution of 1b@(TTF) 1~4 solution; The synthesis method of 2a@(TTF) 1~4 is as follows: First, weigh 12 μmol of the precursor complex palladium(II) 2,2'-bipyridine dinitrate and 8 μmol of TPT, stir them in a 1 mL mixed solution of water and methanol (4:1) at 100 °C for 30 min, filter the remaining product, and freeze-dry the obtained solution to get a pale yellow powder; then weigh 2 μmol of cage powder and 4 mg of TTF, stir them in 1 mL of distilled water at room temperature for 4 h to obtain a 2 μmol / mL 2a@(TTF) 1~4 solution; The synthesis method of 2b@(TTF) is as follows: 1~4 First, weigh 12 μmol of the precursor complex, platinum (II) 2,2'-bipyridine dinitrate, and 8 μmol of TPT. Stir them in a 1 mL mixed solution of water and methanol (4:1) at 100 °C for 4 h. Filter the remaining product and freeze-dry the obtained solution to get a pale yellow powder. Then, weigh 2 μmol of the cage powder and 4 mg of TTF, and stir them in 1 mL of distilled water at room temperature overnight to obtain a 2 μmol / mL solution of 2b@(TTF). 1~4 solution.

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