Oxygen-driven light-conversion nanomaterials, methods of making and using the same

Abstract

This invention discloses oxygen-driven light-conversion nanomaterials, their preparation methods, and applications. The nanomaterials include Au / DPA-MOF composite materials encapsulated in liposomes, with CNTs modified onto the composite material to form Au / MOF / Liposome / CNTs nanomaterials. Compared with the prior art, this invention has the following advantages: (1) The oxygen-driven light-conversion nanomaterials have a better therapeutic effect on tumor cells, and the targeted release of oxygen synergistically enhances their therapeutic efficacy. The selection of fluorescent MOFs makes them ideal materials for in situ cell imaging; (2) The nanomaterials have good biocompatibility.

Description

Technical Field

[0001] This invention belongs to the field of functional nanomaterials technology, and relates to composite materials that can be used for tumor treatment or tumor cell imaging, specifically oxygen-driven light-conversion nanomaterials, their preparation methods, and applications. Background Technology

[0002] Tumor cells can continuously adapt to adverse environments, such as hypoxia. Cellular hypoxia is a pathological phenomenon that occurs when tissues do not receive sufficient oxygen or cannot utilize O2. Under normal circumstances, intracellular O2 is sufficient to meet metabolic needs. However, in tumor tissues, O2 supply is often lower than the cells' growth and metabolic requirements, leading to hypoxia and weakening tumor function. Malignant tumor cells often undergo compensatory processes, resulting not only in resistance to radiation and chemotherapy drugs but also in promoting malignant transformation and metastasis. Furthermore, studies have shown that O2 deficiency in tumor cells alters their gene expression, thus contributing to cancer growth. Therefore, normalizing tumor O2 supply is crucial for combating cancer and other diseases. In recent years, many researchers have proposed various methods to increase O2 concentration in tumors, such as improving tumor blood flow to promote the diffusion of circulating O2 into the tumor to address tumor hypoxia, using smart nanomaterials as oxygen carriers to directly deliver oxygen molecules to the tumor site, and constructing smart nanoplatforms based on the characteristics of the tumor microenvironment to generate O2 in situ within solid tumors. However, each of these methods has its own drawbacks, such as the biotoxicity of nanomaterials and the low oxygen content generated. Summary of the Invention

[0003] Technical problem to be solved: In order to overcome the shortcomings of the existing technology and obtain a composite nanomaterial that can efficiently generate oxygen and is biocompatible, this invention provides oxygen-driven light conversion nanomaterials, their preparation methods and applications.

[0004] Technical solution: Oxygen-driven light-conversion nanomaterials, the nanomaterials comprising Au / DPA-MOF composites encapsulated in liposomes, the composites being modified with CNTs to form Au / MOF / Liposome / CNTs nanomaterials.

[0005] Preferably, the nanomaterial is surface-modified with an antibody, which is a specific recognition antibody for prostate cancer cells LNCAP, or a PSMA antibody.

[0006] The above-described method for preparing oxygen-driven light-conversion nanomaterials includes the following steps:

[0007] S1. Preparation of DPA-MOF

[0008] 9,10-Dianthraylterephthalic acid, zirconium oxychloride octahydrate and benzoic acid were ultrasonically dissolved in N,N-dimethylformamide, and then stirred at 100-120℃. After the reaction was completed, DPA-MOF was collected by centrifugation, washed with DMF and dried.

[0009] S2, Preparation of DPA-MOF-NH2

[0010] 9,10-Dianthraylterephthalic acid, zirconium oxychloride octahydrate and p-aminobenzoic acid were ultrasonically dissolved in N,N-dimethylformamide, and then stirred at 100-120℃. After the reaction was completed, DPA-MOF-NH2 was collected by centrifugation, washed with DMF and dried.

[0011] S3, Synthetic Au / DPA-MOF composite material

[0012] Au nanoparticles were prepared using existing methods. The DPA-MOF-NH2 obtained by S2 was prepared into an aqueous solution of 2-5 mg / mL. Au nanoparticles were then added to the solution, and the mixture was thoroughly mixed by sonication. The product was washed alternately with water and ethanol by centrifugation and dried to obtain the Au / DPA-MOF composite material.

[0013] S4. Synthesis of Au / MOF / Liposome materials

[0014] Dioleoyl lecithin was dissolved in chloroform and dried under a nitrogen stream to obtain a single-layer phospholipid molecular membrane. The membrane was then dissolved in ultrapure water, thoroughly shaken, and allowed to hydrate naturally to obtain a self-assembled Liposome. Subsequently, the membrane was repeatedly extruded using a liposome extruder with a 500 nm filter membrane to obtain Liposomes of the corresponding size.

[0015] The Au / DPA-MOF composite material prepared by S3 was dissolved in ultrapure water, ultrasonically dispersed and centrifuged. The supernatant was added to a container with a single layer of phospholipid molecular film, shaken evenly and naturally hydrated, so that the liposome naturally wrapped the outside of the composite material to form Au / MOF / Liposome material.

[0016] S5. Preparation of Au / MOF / Liposome / CNTs composite materials

[0017] The purchased CNTs were placed in a muffle furnace for calcination and purification, and then added to a container in S4 containing a monolayer phospholipid membrane. Ultrapure water was added, and the mixture was sonicated to dissolve and fully hydrate the CNTs, resulting in a uniform coating of Liposomes on the surface of the CNTs. Subsequently, the CNTs coated with the phospholipid layer were placed in a cell disruptor for ultrasonic cutting, and centrifuged to obtain a CNTs solution of 0.2-0.5 mg / mL. The cut CNTs solution was added to the aqueous solution of Au / MOF / Liposome material prepared in S4, shaken, and allowed to stand naturally for hydration to obtain the Au / MOF / Liposome / CNTs composite material.

[0018] S6. Preparation of Au / MOF / Liposome / CNTs / Antibody nanomotor materials

[0019] Au / MOF / Liposome / CNTs composite material and antibody were incubated in 2-morpholinoethanesulfonic acid buffer, washed with ethanol and dried to obtain Au / MOF / Liposome / CNTs / Antibody nanomotor material.

[0020] Preferably, the molar ratio of 9,10-dianthraylterephthalic acid, zirconium oxychloride octahydrate, and benzoic acid in S1 is 5-10:3-9:82-164.

[0021] Preferably, the molar ratio of 9,10-dianthraylterephthalic acid, zirconium oxychloride octahydrate, and p-aminobenzoic acid in S2 is 5-10:3-9:80-100.

[0022] Preferably, in the preparation of Au nanoparticles, the molar ratio of sodium citrate, citric acid, disodium EDTA, and chloroauric acid is 180-600:120-600:3-30:25; and the molar ratio of DPA-MOF-NH2 to Au nanoparticles is 5-10:1.

[0023] Preferably, the molar ratio of dioleoyl lecithin to chloroform in S4 is 1:5-10; the molar ratio of Au / DPA-MOF composite material to Liposome is 3-10:1.

[0024] Preferably, the volume ratio of the CNTs solution after cutting to the Au / MOF / Liposome material aqueous solution in S5 is 1:3-5.

[0025] Preferably, the mass ratio of Au / MOF / Liposome / CNTs composite material to antibody in S6 is 100-200:1.

[0026] The above-described applications of oxygen-driven light-converting nanomaterials in tumor cell imaging or tumor therapy.

[0027] The working principle of the oxygen-driven light-conversion nanomaterials of this invention is as follows: The method generates nanomaterials in situ. These nanomaterials are designed based on DPA-MOF (oxygen-storing and oxygen-producing) and photosensitizing and thermosensitive Au nanoparticles to create a liposomal nanomotor propelled by oxygen. More preferably, the nanomotor is given targeting properties by outer layer modification with antibodies, enabling the nanomotor to target and continuously supply oxygen to the tumor site, thereby killing tumor cells through the synergistic effect of photodynamic and oxygen supply effects. In this process, tumor cell imaging and multiple therapies can be achieved. Specifically, the anthracene ligand of DPA-MOF in the nanomaterials is a polycyclic aromatic structure that can capture the photosensitizer TCPP and the oxygen generated by the Au nanoparticles. 1 O2 forms an internal peroxide (EPO-MOF), which can revert to its original structure and release O2 under ultraviolet light irradiation, thus achieving oxygen storage and release. Liposomes are coated on the outer layer to improve its biocompatibility, and carbon nanotubes are inserted into the surface of the liposomes to provide oxygen release channels, forming a nanomotor structure with Au / DPA-MOF encapsulated in liposomes as its core. Motion images of this nanomotor were captured using fluorescence microscopy. In vitro cell experiments successfully confirmed the targeted motility and therapeutic effects of the nanomotor. Furthermore, the excellent fluorescence properties of DPA-MOF enabled in vivo fluorescence monitoring, making it an ideal material for treating tumor cells.

[0028] Beneficial effects: (1) The oxygen-driven light conversion nanomaterial has a good therapeutic effect on tumor cells. The targeted release of oxygen further enhances its therapeutic efficacy. The selection of fluorescent MOF makes it an ideal material for in situ cell imaging. (2) The nanomaterial has good biocompatibility. Attached Figure Description

[0029] Figure 1 XRD patterns (a) and infrared spectra (b) of DPA-MOF and Au / DPA-MOF prepared in Example 1;

[0030] Figure 2 Transmission electron microscopy images of DPA-MOF(a), DPA-MOF-NH2(b), Au NPs(c), Au / DPA-MOF(d), Liposome(e), CNTs(f), and Au / MOF / Liposome(gh) prepared for Example 1;

[0031] Figure 3 Bright-field and fluorescence-field images of Liposome (a,b), Au / DPA-MOF (cf), and Au / MOF / Liposome (gh) as described in Example 2;

[0032] Figure 4 The fluorescence spectra of the Au / MOF / Liposome described in Example 3 during photo-oxidation (660nm NIR irradiation) (a) and photolysis (254nm UV irradiation) (b) change over time.

[0033] Figure 5 The fluorescence intensity of Au / DPA-MOF(a) and Au / MOF / Liposome / CNTs(b) after multiple cycles of photo-oxidation and photolysis as described in Example 3;

[0034] Figure 6 The standard curves (a) of DPBF solutions of different concentrations described in Example 4 and the degradation of DPBF over time under near-infrared light irradiation of Au / MOF / Liposome (b) are shown.

[0035] Figure 7 The dissolved oxygen concentrations generated by DPA-MOF, Au / DPA-MOF, Au / MOF / Liposome, and Au / MOF / Liposome / CNTs as described in Example 4 and Comparative Example 1 change over time (a) and the O2 concentrations generated at different Au / DPA-MOF concentrations (b).

[0036] Figure 8 After photo-oxidation and photolysis as described in Example 5, dynamic images of Liposome / Au / MOF / CNTs were captured every 5 seconds.

[0037] Figure 9 The growth of LNCAP cells after adding PBS, DPA-MOF, Au / DPA-MOF, Liposome, Au / MOF / Liposome, CNTs, Au / MOF / Liposome / CNTs, and Au / MOF / Liposome / CNTs / Antibody, as described in Example 6, is shown. Detailed Implementation

[0038] The following embodiments further illustrate the content of the present invention, but should not be construed as limiting the present invention. Modifications and substitutions made to the methods, steps, or conditions of the present invention without departing from the spirit and essence of the invention are all within the scope of the present invention. Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art.

[0039] Example 1

[0040] (1) The preparation method of DPA-MOF includes the following steps:

[0041] 20-40 mg of 9,10-dianthryl terephthalic acid (0.05 mmol), 10-30 mg of zirconium oxychloride octahydrate (ZrOCl2·8H2O, 0.03 mmol), and 100-200 mg of benzoic acid (0.82 mmol) were sonicated and dissolved in 10.0-30.0 mL of N,N-dimethylformamide (DMF), and then sonicated into a 50 mL round-bottom flask. The mixture was stirred at 100-120 °C (500 rpm) for 40-60 min. After the reaction was complete, the DPA-MOF was collected by centrifugation (10000 rpm, 10 min), washed three times with fresh DMF, and dried at 60 °C to obtain the final product.

[0042] (2) Preparation of DPA-MOF-NH2: 20-40 mg of 9,10-dianthraylterephthalic acid (0.05-0.1 mmol), 10-20 mg of zirconium oxychloride octahydrate (ZrOCl2·8H2O, 0.03-0.06 mmol), and 100-130 mg of p-aminobenzoic acid (0.8-1.0 mmol) were ultrasonically dissolved in 10.0-30.0 mL of N,N-dimethylformamide (DMF), and then transferred to a 10 mL round-bottom flask. The mixture was stirred at 100-150 °C (500 rpm) for 1-1.5 h. After the reaction was complete, DPA-MOF-NH2 was collected by centrifugation (10000 rpm, 10-20 min), washed three times with fresh DMF, and dried in a 60 °C oven.

[0043] (3) Synthesis of Au / MOF composite material: 120-160 mL of ultrapure water was added to a three-necked flask and heated to boiling in an oil bath. Then, 3-10 mL of sodium citrate (60 mM) and 2-10 mL of citric acid (60 mM) were added sequentially, and the mixture was stirred at 450 rpm for 30-60 min. Subsequently, 0.1-1.0 mL of disodium ethylenediaminetetraacetate (30 mM) and 1 mL of chloroauric acid (25 mM) were added to the reaction system. The reaction was continued for 3-5 min, and the solution color changed from light yellow to grayish-green, and then to wine red, indicating the successful synthesis of Au NPs. Finally, the three-necked flask was cooled to room temperature in an ice-water bath to obtain Au NPs with a particle size of about 15 nm.

[0044] Subsequently, Au / MOF composite materials were obtained by combining the amino group of DPA-MOF-NH2 with Au. 5-10 mL of Au NPs and 5-10 mL of an aqueous solution (5 mg / L) of DPA-MOF-NH2 were mixed in a 20 mL flask, and then thoroughly mixed under ultrasonic conditions for 1-1.5 h. The resulting solution was centrifuged, washed alternately with water and ethanol, and dried in a 60 °C oven.

[0045] (4) Synthesis of Au / MOF / Liposome: 0.01-0.05 g of dioleoyl lecithin (DOPC) was placed in a 20 mL beaker and dissolved in 2-3 mL of chloroform. The solution was then dried under a nitrogen atmosphere and placed in a vacuum oven at 60 °C overnight to obtain a monolayer phospholipid membrane. This membrane was then dissolved in 5-20 mL of ultrapure water, thoroughly shaken, and allowed to stand for 30-60 min to allow for natural hydration, resulting in a self-assembled Liposome. This Liposome was then repeatedly extruded more than 10 times using a liposome extruder with a 500 nm filter membrane to obtain Liposome materials with a size of approximately 500 nm.

[0046] Dissolve 0.03-0.1g of Au / MOF composite material in 1.5-3.0mL of ultrapure water, and use ultrasound to assist dissolution for 30-60min to ensure uniform dispersion of the composite material. After centrifugation at 1000r / min, collect the supernatant and add it to a beaker with a single layer of phospholipids on the wall, shake well, and allow it to hydrate naturally for 30-60min. Liposomes will naturally coat the outside of the composite material, forming the desired Au / MOF / Liposome material.

[0047] (5) Preparation of Au / MOF / Liposome / CNTs composite material: First, the purchased CNTs were placed in a muffle furnace and calcined at 500-600℃ for 8 hours to obtain purified CNTs. Next, they were added to a beaker with a monolayer of phospholipids on the wall, and 2-5 mL of ultrapure water was added. The beaker was sonicated for 30-60 minutes to ensure full hydration and uniform coating of phospholipids on the surface of the CNTs. Subsequently, the CNTs solution coated with the phospholipid layer was placed in a 50 mL beaker, and 30-50 mL of pure water was added. The beaker was then sonicated in a cell disruptor for 10-14 hours. Finally, the beaker was centrifuged at 8000 r / min to obtain a CNTs solution with a concentration of 0.2-0.5 mg / mL. The cut CNTs solution was added to an aqueous solution containing Au / MOF / Liposome material, shaken well, and allowed to stand for 30-60 minutes to allow it to hydrate naturally, thus obtaining the desired Au / MOF / Liposome / CNTs material.

[0048] (6) Synthesis of Au / MOF / Liposome / CNTs / Antibody composite material: Au / MOF / Liposome / CNTs / Antibody was prepared by incubation method. 2-10 mL of Au / MOF / Liposome / CNTs solution was incubated with 50-80 mL of 2-morpholinoethanesulfonic acid (MES) buffer of Antibody for 1-1.5 h, followed by washing with ethanol and drying.

[0049] XRD analysis was performed on the prepared DPA-MOF and Au / MOF to characterize their crystallinity and morphology. The results are as follows: Figure 1 As shown in (a), the prepared DPA-MOF has a good crystal structure, and the main characteristic peaks are consistent with the literature description, indicating the successful synthesis of DPA-MOF. Compared with DPA-MOF, the crystal structure of Au / DPA-MOF is basically unchanged, with only two additional characteristic peaks at 38.2° and 44.4°, which correspond to the (400) and (331) crystal planes of Au nanoparticles, indicating the successful preparation of Au / DPA-MOF material. Furthermore, the structure of DPA-MOF remains stable after modification with Au nanoparticles. The FTIR spectra of DPA-MOF and Au / DPA-MOF are shown below. Figure 1 As shown in (b). DPA-MOF at 3440cm -1 2920cm -1 1660cm -1 1610cm -1 1410cm -1 1260cm -1 1100cm -1 765cm -1 and 660cm -1 Characteristic absorption peaks appear, with one at 3440 cm⁻¹. -1 The broad absorption peak at 2920 cm⁻¹ is caused by the stretching vibration of the OH bond in the hydroxyl group. -1 The characteristic peak at 1610 cm⁻¹ is caused by the stretching vibration of the methylene group. -1 and 1660cm -1 The sharp absorption peak at 1410 cm⁻¹ is a result of the stretching vibration of the carbon-carbon double bond. -1 The absorption peak at 765 cm⁻¹ indicates the in-plane bending vibration of the carbon-hydrogen bond. -1 and 660cm -1 These peaks represent bending vibrations of the benzene ring. The appearance of these characteristic peaks indicates the successful synthesis of DPA-MOF. The characteristic peaks of Au / DPA-MOF are essentially the same as those of DPA-MOF, indicating that the structure of DPA-MOF did not change significantly before and after Au NPs modification, and that the Au / DPA-MOF composite material was successfully prepared.

[0050] Figure 2Images (a), (b)-(c) are TEM images of Au nanoparticles and DPA-MOF, respectively. The images show that uniformly sized Au nanoparticles and well-morphologically formed DPA-MOF materials were successfully prepared. The Au nanoparticles have a diameter of approximately 15 nm, while the DPA-MOF particles have a diameter of approximately 150 nm. The Au / DPA-MOF was prepared based on the bonding of the amino group of DPA-MOF with Au. Figure 2 (d) It can be seen that Au nanoparticles are uniformly modified on the surface of DPA-MOF. After modification with Au nanoparticles, the size of DPA-MOF increases significantly to approximately 350 nm. This may be because some Au nanoparticles are adsorbed in the pores of DPA-MOF, resulting in an increase in particle size. Figure 2 As shown in (e), after staining the prepared liposomes with phosphotungstic acid, the morphology of the liposomes can be clearly observed, with a size of approximately 500 nm. Purified and cut purchased carbon nanotubes were placed in a small beaker with a phospholipid film on the wall. Through natural hydration, CNTs with an outer phospholipid coating were obtained, allowing for better integration with the liposomes. After coating the CNTs with phospholipid, they were ultrasonically cut again to obtain CNT materials with a diameter of approximately 30 nm. Figure 2 As shown in (f). However, after internal coating with materials, the size of Au / MOF / Liposome increases to approximately 1 μm, and its shape changes from spherical to irregular. This is likely due to its good flowability, such as... Figure 2 As shown in (g)-(h).

[0051] To further characterize the successful preparation of Au / MOF / Liposome, CNTs, Au / DPA-MOF, Liposome, and Au / MOF / Liposome were observed at 40x field of view using an inverted fluorescence microscope. Figure 3 Images (a)-(b) show individual Liposomes under a fluorescence microscope. It is clearly visible that under bright field, the Liposomes possess a phospholipid bilayer structure, and the prepared Liposomes are relatively uniform in size. However, under fluorescence field, no fluorescence is observed in the Liposomes, indicating that they do not possess fluorescent properties. Next, the imaging effect of Au / DPA-MOF under a fluorescence microscope was tested, as shown below. Figure 3 As shown in (c)-(f), under blue fluorescence excitation, the material clearly emits a distinct green fluorescence, indicating its excellent fluorescence performance. Furthermore, its particle size is consistent with the TEM test data, approximately 350 nm. After coating the surface with liposomes, bright-field imaging... Figure 3(g) It can be observed that the structure of Au / MOF / Liposome has changed, no longer possessing a regular spherical structure, which may be due to the fluidity of the liposomes. In the fluorescence field image, it can be seen that the Liposome encapsulating Au / DPA-MOF emits obvious fluorescence under blue light excitation, proving that Au / MOF was successfully encapsulated within the Liposome.

[0052] Example 2

[0053] Methods for investigating the absorption and oxygen production performance of Au / MOF / Liposome / CNTs: DPA-MOF is a polycyclic aromatic hydrocarbon complex that can capture singlet oxygen under certain conditions. 1 O2 forms an internal peroxide complex (EPO-MOF), a process known as photooxidation. Under heating or ultraviolet light irradiation, EPO-MOF releases O2 and reverts to its original DPA structure, thus achieving O2 storage and release; this is called photolysis. During this process, there is a decrease in fluorescence intensity between DPA-MOF and EPO-MOF, and an increase in fluorescence intensity between EPO-MOF and DPA-MOF. Therefore, monitoring the changes in fluorescence intensity of Au / MOF / Liposome under different visible light irradiation times verifies the structural transformation of DPA-MOF.

[0054] like Figure 4 The figures show the fluorescence intensity of Au / MOF / Liposome as a function of visible light (660 nm) and ultraviolet light (365 nm) irradiation time, respectively. It can be seen that the fluorescence intensity of Au / MOF / Liposome gradually decreases with increasing visible light irradiation time, reaching its lowest point at 120 min. However, after ultraviolet light irradiation, its fluorescence intensity gradually increases over time, with little change after 120 min, demonstrating structural changes and recovery. The encapsulation of Liposome only slightly affects its fluorescence intensity, possibly because the phospholipid bilayer of Liposome provides some insulation against the fluorescence intensity of the internal material.

[0055] Example 3

[0056] Methods for investigating the recyclability of Au / MOF / Liposome / CNTs composites: To investigate the recyclability of the materials, cyclic tests were conducted on the photo-oxidation and photolysis processes of Au / DPA-MOF and Au / MOF / Liposome / CNTs, such as... Figure 5 As shown, Figure 5(a)-(b) represent the fluorescence intensity changes after five cycles of photooxidation and photolysis of Au / DPA-MOF and Au / MOF / Liposome / CNTs, respectively. It can be seen that the fluorescence performance of Au / MOF decreases significantly in the first cycle, but remains relatively stable in the subsequent four cycles, indicating its excellent fluorescence properties and stability. However, after encapsulating Liposomes and CNTs, the fluorescence intensity still decreases significantly after the first cycle, but remains stable after the next three cycles. A significant decrease in fluorescence occurs in the fifth cycle, which may be due to the partial breakage of the outer liposome coating, thus affecting its fluorescence performance.

[0057] Example 4

[0058] Methods for investigating the photodynamic properties of Au / MOF / Liposome / CNTs composites: First, 1,3-diphenylisobenzofuran (DPBF solutions) of different concentrations were prepared, and their absorbance was measured to plot a standard curve. Then, the different materials being tested (200 μg / mL) were added to a 0.3 mM DPBF solution and irradiated with 660 nm visible light. The supernatant was collected every 20 seconds within the 0-150 s range, and its absorbance was measured. The change in absorbance value represents the photodynamic properties. 1 O2 generation capability. Figure 6 (a)-(b) show the standard curve of DPBF concentration versus absorbance and the UV spectrum of DPBF absorbance over time. It can be seen that the absorbance of DPBF gradually decreases over time, indicating that the concentration gradually decreases. 1 The gradual generation of O2.

[0059] Example 5

[0060] Methods for investigating O2 generation: The changes in dissolved oxygen concentration in DPA-MOF, Au / DPA-MOF, Au / MOF / Liposome, and Au / MOF / Liposome / CNTs during the photolysis reaction were measured using a dissolved oxygen analyzer. Figure 7(a) shows the O2 content of different materials during the photolysis process. It can be seen that the O2 concentration in the DPA-MOF solution alone remained essentially unchanged over time, indicating that DPA-MOF alone does not have the ability to generate O2. The Au / DPA-MOF solution had the highest O2 concentration, followed by Au / MOF / Liposome / CNTs. The O2 content in Au / MOF / Liposome increased by only half that of Au / DPA-MOF, indicating that the Liposome encapsulation had a certain blocking effect on O2 generation and release. However, the insertion of CNTs provided a channel for O2 generation and release, allowing it to be emitted through the CNTs. Therefore, the O2 content in Au / MOF / Liposome / CNTs increased compared to Au / MOF / Liposome. Without encapsulation by other materials, Au / DPA-MOF had the highest oxygen production, reaching 12 mg / L, which provided the main driving force for the subsequent movement of the nanomotor.

[0061] To verify that the oxygen in Au / MOF / Liposome / CNTs is generated by Au / DPA-MOF, the O2 content of Au / DPA-MOF with different dosages was tested, such as... Figure 7 As shown in (b), the dissolved oxygen content in the Au / MOF / Liposome / CNTs solution as a function of UV irradiation time was tested when the Au / DPA-MOF content was 0, 10 mM, 30 mM, and 50 mM, respectively. Figure 7 As can be clearly seen in (b), the higher the content of Au / DPA-MOF over time, the higher the content of O2 generated within it, indicating that the O2 content generated in the system is positively correlated with Au / DPA-MOF. Therefore, the photolysis process of Au / DPA-MOF is the main source of O2 generation.

[0062] Example 6

[0063] Methods for investigating the performance of Au / MOF / Liposome / CNT nanomotors: Based on the oxygen-generating characteristics of Au / MOF / Liposome / CNT nanomotors, their mobility in photo-oxidation and photolysis processes was investigated. Their trajectories were recorded using an inverted fluorescence microscope, as shown below. Figure 8 The images shown are taken at 5-second intervals during the photo-oxidation and photolysis stages of the nanomotor. It can be seen that during the photo-oxidation stage, since this process only involves... 1 The nanomotor generates and absorbs O2, but does not produce O2; therefore, it lacks mobility and its position remains unchanged after 60 seconds of capture. During the photolysis phase, the nanomotor absorbs... 1O2 releases O2, thus O2 acts as a driving force to propel the nanomotor. This motion can be observed under an inverted fluorescence microscope. After 60 seconds of capture, its position under the microscope gradually changes over time, demonstrating the nanomotor's excellent movement capability. Fluorescence images observed under a fluorescence field clearly show that the nanomotor emits bright green light under blue light excitation. When superimposed with bright-field images, the bright-field and fluorescence images overlap, confirming its excellent movement capability and fluorescence effect.

[0064] Example 7

[0065] The method for investigating the therapeutic effect of Au / MOF / Liposome / CNTs / PSMA-Antibody composite materials on tumor cells: First, its motility and imaging ability within LNCAP cells were tested. PBS, DPA-MOF, Au / DPA-MOF, Liposome, Au / MOF / Liposome, CNTs, Au / MOF / Liposome / CNTs, and Au / MOF / Liposome / CNTs / PSMA-Antibody were added to tumor cells and incubated together for 4-6 hours, followed by irradiation with visible light and near-infrared light for 2-4 hours respectively, and then incubated together for 20-24 hours. Images were then observed using an inverted fluorescence microscope. Figure 9The figures show the growth of cells in the blank group (with PBS) and cells incubated with various materials and exposed to visible and ultraviolet light after 20-24 hours of culture. As can be seen from the figures, when incubated with only PBS and no materials, the cells were evenly distributed in the microscope field of view and grew well. No fluorescence was observed under a fluorescence field, proving that individual cells do not produce fluorescence. After adding DPA-MOF alone and irradiating with visible / near-infrared light, the material gradually entered the cells due to endocytosis between the materials and the cells. Switching to a fluorescence field, bright green light was clearly visible when the cells were excited by blue light, proving the successful integration of DPA-MOF with the cells. However, cell growth was not significantly inhibited, indicating that DPA-MOF alone has no killing effect on LNCAP cells. After adding Liposomes or CNTs, the cells grew well, and no fluorescence was observed under a fluorescence field, proving that Liposomes and CNTs have good biocompatibility and do not fluoresce on their own. After the addition of Au / DPA-MOF, under the action of the photosensitizer, DPA-MOF begins to undergo photo-oxidation and photolysis, generating a large amount of O2. This O2 supply oxygen to the tumor site, thus killing LNCAP cells. A significant inhibition of LNCAP cell growth and a substantial reduction in cell number were observed. Switching to a fluorescence field revealed obvious cell fluorescence, confirming that the growth inhibition was due to the Au / DPA-MOF material. In contrast, the cell number in the Au / MOF / Liposome group was only slightly reduced compared to the control group, demonstrating that the good biocompatibility of Liposomes provides some protection for the cells. The encapsulation of Au / DPA-MOF within the Liposome significantly reduces toxicity. Similarly, obvious fluorescence was observed under a fluorescence field, indicating the material's excellent fluorescence effect and successful cell entry. After the addition of Au / MOF / Liposome / CNTs, the number of cells increased significantly compared to the Au / MOF / Liposome group. This is because the introduction of CNT channels enabled the successful diffusion of O2 generated by Au / DPA-MOF. After undergoing photo-oxidation and photolysis processes, the nanomotors began to generate O2 and moved under the impetus of O2, supplying oxygen to the hypoxic areas of tumor cells and generating... 1O2 synergistically enhances the therapeutic effect on tumor cells, demonstrating the excellent inhibitory effect of nanomotors on tumor cells. Cell activity was significantly reduced. Even after switching to a fluorescence field, the cells still emitted significant fluorescence, confirming their excellent fluorescence properties and therapeutic efficacy. Finally, after adding Au / MOF / Liposome / CNTs / Antibody and irradiating with visible / near-infrared light, cell growth was further inhibited under a bright-field inverted fluorescence microscope, and significant fluorescence was observed under a fluorescence field. Compared to unmodified antibody-based nanomotors, the antibody-modified nanomotors can target and move to the tumor site through the interaction between the outer antibody and intracellular antigens, inhibiting tumor cell growth through in-situ oxygen supply and the synergistic photothermal and photodynamic effects of Au nanoparticles. In-situ fluorescence imaging under a fluorescence field also allows for real-time monitoring of cell number changes, demonstrating the excellent targeted tumor therapy capability and good fluorescence imaging effect of the nanomotors.

Claims

1. An oxygen-driven light-converting nanomaterial, characterized in that, The nanomaterials include Au / DPA-MOF composite materials encapsulated in liposomes, with CNTs modified on the composite materials to form Au / MOF / Liposome / CNTs nanomaterials; The oxygen-driven light-conversion nanomaterial is prepared by the following method, including the following steps: S1. Preparation of DPA-MOF 9,10-Dianthraylterephthalic acid, zirconium oxychloride octahydrate and benzoic acid were ultrasonically dissolved in N,N-dimethylformamide, and then stirred at 100-120℃. After the reaction was completed, DPA-MOF was collected by centrifugation, washed with DMF and dried. S2, Preparation of DPA-MOF-NH2 9,10-Dianthraylterephthalic acid, zirconium oxychloride octahydrate and p-aminobenzoic acid were ultrasonically dissolved in N,N-dimethylformamide, and then stirred at 100-120℃. After the reaction was completed, DPA-MOF-NH2 was collected by centrifugation, washed with DMF and dried. S3, Synthetic Au / DPA-MOF composite material Au nanoparticles were prepared using existing methods. The DPA-MOF-NH2 obtained by S2 was prepared into an aqueous solution of 2-5 mg / mL. Au nanoparticles were then added to the solution, and the mixture was thoroughly mixed by sonication. The product was washed alternately with water and ethanol by centrifugation and dried to obtain the Au / DPA-MOF composite material. S4. Synthesis of Au / MOF / Liposome materials Dioleoyl lecithin was dissolved in chloroform and dried under a nitrogen stream to obtain a single-layer phospholipid molecular membrane. The membrane was then dissolved in ultrapure water, thoroughly shaken, and allowed to hydrate naturally to obtain a self-assembled Liposome. Subsequently, the membrane was repeatedly extruded using a liposome extruder with a 500 nm filter membrane to obtain Liposomes of the corresponding size. The Au / DPA-MOF composite material prepared by S3 was dissolved in ultrapure water, ultrasonically dispersed and centrifuged. The supernatant was added to a container with a single layer of phospholipid molecular film, shaken evenly and naturally hydrated, so that the liposome naturally wrapped the outside of the composite material to form Au / MOF / Liposome material. S5. Preparation of Au / MOF / Liposome / CNTs composite materials The purchased CNTs were placed in a muffle furnace for calcination and purification, and then added to a container in S4 containing a monolayer phospholipid membrane. Ultrapure water was added, and the mixture was sonicated to dissolve and fully hydrate the CNTs, resulting in a uniform coating of Liposomes on the surface of the CNTs. Subsequently, the CNTs coated with the phospholipid layer were placed in a cell disruptor for ultrasonic cutting, and centrifuged to obtain a CNTs solution of 0.2-0.5 mg / mL. The cut CNTs solution was added to the aqueous solution of Au / MOF / Liposome material prepared in S4, shaken, and allowed to stand naturally for hydration to obtain the Au / MOF / Liposome / CNTs composite material. S6. Preparation of Au / MOF / Liposome / CNTs / Antibody nanomotor materials Au / MOF / Liposome / CNTs composite material and antibody were incubated in 2-morpholinoethanesulfonic acid buffer, washed with ethanol and dried to obtain Au / MOF / Liposome / CNTs / Antibody nanomotor material.

2. The oxygen-driven light-conversion nanomaterial according to claim 1, characterized in that, The nanomaterial is surface-modified with an antibody, which is a specific recognition antibody for prostate cancer cells LNCAP, specifically a PSMA antibody.

3. The oxygen-driven light-conversion nanomaterial according to claim 1, characterized in that, The molar ratio of 9,10-dianthraylterephthalic acid, zirconium oxychloride octahydrate, and benzoic acid in S1 is 5-10:3-9:82-164.

4. The oxygen-driven light-conversion nanomaterial according to claim 1, characterized in that, The molar ratio of 9,10-dianthraylterephthalic acid, zirconium oxychloride octahydrate, and p-aminobenzoic acid in S2 is 5-10:3-9:80-100.

5. The oxygen-driven light-conversion nanomaterial according to claim 1, characterized in that, In the preparation of Au nanoparticles, the molar ratio of sodium citrate, citric acid, disodium EDTA and chloroauric acid is 180-600:120-600:3-30:

25. The volume ratio of DPA-MOF-NH2 to Au nanoparticles is 5-10:

1.

6. The oxygen-driven light-conversion nanomaterial according to claim 1, characterized in that, The molar ratio of dioleoyl lecithin to chloroform in S4 is 1:5-10; the molar ratio of Au / DPA-MOF composite material to Liposome is 3-10:

1.

7. The oxygen-driven light-conversion nanomaterial according to claim 1, characterized in that, The volume ratio of the cut CNTs solution to the Au / MOF / Liposome material aqueous solution in S5 is 1:3-5.

8. The oxygen-driven light-conversion nanomaterial according to claim 1, characterized in that, The mass ratio of Au / MOF / Liposome / CNTs composite material to antibody in S6 is 100-200:

1.

9. The use of the oxygen-driven light-conversion nanomaterial of claim 1 in the preparation of tumor cell imaging reagents or tumor therapeutic drugs.

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