A type of ultra-small hydrogen-molybdenum bronze H x MoO3 nanomaterials, their preparation methods and applications

Abstract

This invention discloses an ultra-small size hydrogen-molybdenum bronze (H x A method for preparing MoO3 nanomaterials (average particle size ≤ 10 nm) is disclosed. This method first involves the reduction intercalation of molybdenum oxide with an aluminum / acid aqueous solution to synthesize nanoscale hydrogen-molybdenum bronze; then, the resulting product is subjected to controlled ultrasonic fragmentation to obtain ultrasmall hydrogen-molybdenum bronze nanoparticles. This method is simple and efficient, possessing good potential for large-scale production. Experiments show that the ultrasmall hydrogen-molybdenum bronze nanomaterials prepared in this invention exhibit excellent scavenging ability of reactive oxygen species and nitrogenous substances (RONS) and significant passive targeted enrichment characteristics in the kidneys, demonstrating outstanding application value in the treatment of kidney injury.

Description

Technical Field

[0001] This invention belongs to the field of nanomaterials and biomedicine, specifically relating to an ultra-small hydrogen-molybdenum bronze (H). x MoO3 nanoparticles, their preparation methods, and applications. MoO3 nanoparticles with an average particle size ≤ 10 nm were prepared using aluminum / acid reduction intercalation combined with controlled ultrasonic fragmentation technology. x Controllable preparation of MoO3. This material has significant biological effects and application prospects in anti-tumor therapy, inflammatory bowel disease (IBD) treatment, and protection against kidney injury. Background Technology

[0002] Acute kidney injury (AKI) is a clinical syndrome accompanied by various critical illnesses, characterized by a rapid decline in glomerular filtration rate and excretory function, affecting approximately 15% of hospitalized adults and 25% of hospitalized children, and significantly increasing mortality and the risk of chronic renal insufficiency. Studies have shown that excessive production of reactive nitrogen oxides not only induces apoptosis of renal tubular epithelial cells through oxidative damage to nucleic acids, lipids, and proteins, but also activates inflammatory pathways such as NF-κB and drives the expression of fibrosis genes, becoming a key factor in the progression of AKI. Currently, there are no effective treatments available in clinical practice, making the treatment of AKI a significant clinical challenge.

[0003] In recent years, hydrogen has shown significant protective effects in kidney injury. Its main mechanism involves the selective scavenging of highly reactive RONS such as ·OH and ONOO⁺, thereby reducing oxidative stress levels, activating the endogenous antioxidant system, and inhibiting inflammatory responses. Furthermore, hydrogen exhibits good biocompatibility and excellent tissue diffusion capabilities, allowing it to penetrate intracellular and subcellular structures. However, as an inert gas, the radiation protection mechanism of hydrogen in vivo is not fully understood. It has been reported that hydrogen can be cleaved into hydrogen atoms with higher reducing activity under the catalysis of endogenous metalloenzymes such as iron porphyrin, thus exerting a synergistic RONS scavenging function. However, due to the limitations of the glomerular filtration barrier and the short lifespan of reactive hydrogen, the efficient delivery of hydrogen or its reactive hydrogen to the site of kidney injury remains challenging.

[0004] Hydrogen molybdenum bronze (H x MoO3 (MoO3) belongs to a class of non-stoichiometric molybdenum-based oxide functional materials. Its core characteristic lies in the reversible insertion and extraction of active hydrogen (H·) into and out of the crystal lattice, forming a unique hydrogen intercalation compound structure. This reversible hydrogen insertion / extraction kinetics is the fundamental source of the material's significant redox activity. x MoO3 typically exhibits a mixed valence state (MoO3) 4 ⁺ / Mo 5 ⁺ Coexistence), its specific chemical state (including key physicochemical properties such as band structure, work function, and conductivity) can be flexibly optimized by precisely controlling the amount of hydrogen intercalation (x value). Based on the above characteristics, Hx MoO3 has shown significant application potential in electrochemical hydrogen / energy storage, electrocatalysis, and electrochemical devices. However, currently reported micro / nano H2O... x MoO3 material particles are much larger than the size filtration threshold of the glomerular filtration barrier in the kidney, which makes it impossible for them to effectively penetrate the barrier and achieve efficient passive targeted enrichment at the site of kidney injury (such as the renal tubules). Even if the material itself has the potential to clear reactive oxygen species (RONS), it is difficult to exert its in vivo kidney therapeutic performance because it cannot reach an effective therapeutic concentration at the lesion.

[0005] Therefore, there is an urgent need to develop a nanomaterial that combines ultra-small particle size with highly efficient RONS scavenging ability and passive targeted enrichment in the kidneys to meet the clinical needs of kidney injury treatment. This invention provides an ultra-small hydrogen-molybdenum bronze (H2B) with an average particle size ≤10 nm. x The preparation method of MoO3 nanomaterials not only realizes the large-scale synthesis of materials, but also endows them with superior passive kidney targeting properties, providing a new strategy for the effective treatment of acute kidney injury.

[0006] Definitions of terms in this invention:

[0007] H x MoO3 is short for Hydrogen molybdenum bronze; RONS stands for Reactive Oxygen and Nitrogen Species.

[0008] abbreviation;

[0009] MoO3 is the abbreviation for molybdenum trioxide.

[0010] PBS is short for Phosphate Buffered Saline.

[0011] Molybdenum trioxide: The molybdenum trioxide configuration used in this invention includes α-MoO 3、 h-MoO3, etc. Summary of the Invention

[0012] To address the technical problems of low hydrogen delivery efficiency and inability to overcome the glomerular filtration barrier in existing hydrogen therapy for kidney injury, this invention provides a method based on ultra-small-sized hydrogen-molybdenum bronze (H x MoO3 (particle size ≤ 10 nm) nanomaterials form a highly efficient kidney-targeted hydrogen delivery system. This material utilizes a size-dependent glomerular filtration effect to specifically deliver active hydrogen to the site of kidney injury, significantly improving therapeutic efficacy.

[0013] The ultra-small size H described in this invention x MoO3 nanoparticles, x = 0.01 ~ 2.58.

[0014] The second objective of this invention is to provide an H x Synthesis method of MoO3 nanomaterials.

[0015] The third objective of this invention is to provide an ultra-small H-type process that is simple to implement and easy to scale up. x Synthesis method of MoO3.

[0016] The fourth objective of this invention is to provide an ultra-small H x The application of MoO3 nanomaterials in the treatment of acute kidney injury, due to the ultra-small size effect H x MoO3 can cross the glomerular filtration barrier, efficiently delivering active hydrogen to the site of kidney injury, making it suitable for the treatment of acute kidney injury.

[0017] This invention describes an ultra-small H x The preparation method of MoO3 nanomaterials includes the following steps:

[0018] Step 1: Add molybdenum trioxide (α-MoO3 or h-MoO3) to an acidic solution containing hydrogen protons, and add elemental aluminum as a reducing agent to carry out a reduction intercalation reaction. After the reaction is completed, the solution is purified by centrifugation, washed, and vacuum dried to obtain hydrogen molybdenum bronze (H). x MoO3 nanoparticles.

[0019] Step 2: Take the H obtained in Step 1 x MoO3 nanoparticles were dispersed in an aqueous medium, treated by ultrasonic disruption, and then separated by ultracentrifugation to obtain H nanoparticles with an average particle size ≤ 10 nm. x MoO3 nanoparticles.

[0020] Among them, ultrasonic disruption uses a controllable ultrasonic disruptor, including a cell disruptor.

[0021] Furthermore, in step one, the acidic solution containing hydrogen protons is selected from any one or more of hydrochloric acid, sulfuric acid, nitric acid, trifluoroacetic acid, acetic acid, and hydrofluoric acid; wherein the volume ratio of acid to water is 1:9 to 9:1.

[0022] Further, in step one, the elemental aluminum is aluminum foil (thickness 0.01 ~ 0.5 mm) or aluminum powder (particle size 100 nm ~ 100 µm), and the mass ratio of elemental aluminum to MoO3 is (0.1 ~ 5): 1.

[0023] Furthermore, in step one, the temperature of the reduction intercalation reaction is 0 ~ 60°C, and the reaction time is 0.5 ~ 48 hours.

[0024] Further, in step two, the characteristic is that the ultrasonic disruption medium is deionized water or phosphate buffer (PBS, pH 7.0 ~ 7.4); the ultrasonic disruption uses a probe-type disruptor; the power is 100-800 W, the frequency is 20 ~ 40 kHz, the ultrasonic disruption uses a pulse mode (on / off duration ratio 1:1 ~ 1:4); and the time is 0.5 ~ 12 hours.

[0025] Furthermore, the ultra-small H described in this invention x MoO3 nanomaterials and their preparation methods can be used for diseases such as tumors, inflammatory bowel disease, and kidney injury, including applications in the preparation of drugs and devices related to the treatment / prevention / detection of tumors, inflammatory bowel disease, and kidney injury. Furthermore, this invention provides ultra-small H... x MoO3 nanomaterials can be used in the treatment of acute kidney injury.

[0026] Furthermore, the present invention has an ultra-small H x MoO3 nanomaterial I has, but is not limited to, the following advantages:

[0027] (1) Due to the size effect, it can pass through the glomerular filtration barrier;

[0028] (2) It exhibits excellent controllable degradation characteristics under physiological conditions, effectively avoids accumulation in the body, and significantly improves biosafety. Attached Figure Description

[0029] Figure 1 It's a super small H x TEM (a) and particle size distribution (b) of MoO3 nanomaterials;

[0030] Figure 2 It's a super small H x XRD pattern of MoO3 nanomaterials;

[0031] Figure 3 It's a super small H x MoO3 nanomaterials remove ·OH (a), H2O2 (b), and ·O2. ¯ (c) and ONOO ¯ (d) performance;

[0032] Figure 4 Different concentrations of ultra-small H x NRK-52E cell survival rate after treatment with MoO3 nanomaterials;

[0033] Figure 5 It's a super small H xCellular therapeutic properties of MoO3 nanomaterials against cisplatin-damaged cells;

[0034] Figure 6 These are different treatment groups (normal group, cisplatin (DPP), DPP+H) x Intracellular RONS levels in MoO3 cells;

[0035] Figure 7 These are different treatment groups (normal group, cisplatin (DPP), DPP+H) x γ-H2AX immunofluorescence image of MoO3 DNA double-strand breaks;

[0036] Figure 8 It's a super small H x Biocompatibility of MoO3 nanomaterials. Detailed Implementation

[0037] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments, but this is not intended to limit the scope of protection of the present invention.

[0038] Example 1: Ultra-small hydrogen-molybdenum bronze (H x Preparation of MoO3

[0039] Step 1: Add 200 mg of α-MoO3 to 6 mL of an aqueous solution containing hydrochloric acid (V(HCl):V(H2O) = 1:2), and add 100 mg of aluminum foil in several batches while stirring at room temperature. After the reaction is complete, centrifuge, wash, and vacuum dry to obtain hydrogen molybdenum bronze (H2O). x MoO3 nanoparticles.

[0040] Step 2: Add 100 mg H x MoO3 was dispersed in 30 mL of ultrapure water and sonicated for 4 hours using a cell disruptor with the following parameters: power 390 W, frequency 20 kHz, sonication time 5 s, interval 5 s, and total time 4 h. H2 was removed by centrifugation. x MoO3 nanomaterials, supernatant lyophilized to obtain ultrasmall H x MoO3.

[0041] Example 2: Ultra-small hydrogen-molybdenum bronze (H x Preparation of MoO3

[0042] Step 1: Add 200 mg of α-MoO3 to 6 mL of an aqueous solution containing hydrochloric acid (V(HCl):V(H2O) = 1:5), and add 100 mg of aluminum foil in several batches while stirring at room temperature. After the reaction is complete, centrifuge, wash, and vacuum dry to obtain hydrogen molybdenum bronze (H2O). x MoO3 nanoparticles.

[0043] Step 2: Add 100 mg H x MoO3 was dispersed in 30 mL of ultrapure water and sonicated for 4 hours using a cell disruptor with the following parameters: power 390 W, frequency 20 kHz, sonication time 5 s, interval 5 s, and total time 4 h. H2 was removed by centrifugation. x MoO3 nanomaterials, supernatant lyophilized to obtain ultrasmall H x MoO3.

[0044] Example 3: Ultra-small hydrogen-molybdenum bronze (H x Preparation of MoO3

[0045] Step 1: Add 200 mg of α-MoO3 to 6 mL of an aqueous solution containing hydrochloric acid (V(HCl):V(H2O) = 1:9), and add 20 mg of aluminum powder in several batches while stirring at room temperature. After the reaction is complete, centrifuge, wash, and vacuum dry to obtain hydrogen molybdenum bronze (H2O). x MoO3 nanoparticles.

[0046] Step 2: Add 100 mg H x MoO3 was dispersed in 30 mL of ultrapure water and sonicated for 4 hours using a cell disruptor with the following parameters: power 390 W, frequency 20 kHz, sonication time 5 s, interval 5 s, and total time 4 h. H2 was removed by centrifugation. x MoO3 nanomaterials, supernatant lyophilized to obtain ultrasmall H x MoO3.

[0047] Example 4: Ultra-small hydrogen-molybdenum bronze (H x Preparation of MoO3

[0048] Step 1: Add 200 mg of α-MoO3 to 6 mL of an aqueous solution containing hydrochloric acid (V(HCl):V(H2O) = 1:1), and add 200 mg of aluminum foil in multiple batches while stirring at 60 °C. After the reaction is complete, centrifuge, wash, and vacuum dry to obtain hydrogen molybdenum bronze (H2O). x MoO3 nanoparticles.

[0049] Step 2: Add 100 mg H x MoO3 was dispersed in 30 mL of ultrapure water and sonicated for 4 hours using a cell disruptor with the following parameters: power 390 W, frequency 20 kHz, sonication time 5 s, interval 5 s, and total time 4 h. H2 was removed by centrifugation. x MoO3 nanomaterials, supernatant lyophilized to obtain ultrasmall H x MoO3.

[0050] Example 5: Ultra-small hydrogen-molybdenum bronze (H xPreparation of MoO3

[0051] Step 1: Add 200 mg of α-MoO3 to 6 mL of an aqueous solution containing hydrochloric acid (V(HCl):V(H2O) = 2:1), and add 100 mg of aluminum foil in multiple batches while stirring at 0°C. After the reaction is complete, centrifuge, wash, and vacuum dry to obtain hydrogen molybdenum bronze (H2O). x MoO3 nanoparticles.

[0052] Step 2: Add 100 mg H x MoO3 was dispersed in 30 mL of ultrapure water and sonicated for 4 hours using a cell disruptor with the following parameters: power 390 W, frequency 20 kHz, sonication time 5 s, interval 5 s, and total time 4 h. H2 was removed by centrifugation. x MoO3 nanomaterials, supernatant lyophilized to obtain ultrasmall H x MoO3.

[0053] Example 6 Ultra-small hydrogen-molybdenum bronze (H x Preparation of MoO3

[0054] Step 1: Add 200 mg of h-MoO3 to 6 mL of an aqueous solution containing hydrochloric acid (V(HCl):V(H2O) = 5:1), and add 1000 mg of aluminum powder in several batches while stirring at room temperature. After the reaction is complete, centrifuge, wash, and vacuum dry to obtain hydrogen molybdenum bronze (H2O). x MoO3 nanoparticles.

[0055] Step 2: Add 100 mg H x MoO3 was dispersed in 30 mL of ultrapure water and sonicated for 4 hours using a cell disruptor with the following parameters: power 390 W, frequency 20 kHz, sonication time 5 s, interval 5 s, and total time 4 h. H2 was removed by centrifugation. x MoO3 nanomaterials, supernatant lyophilized to obtain ultrasmall H x MoO3.

[0056] Example 7 Ultra-small hydrogen-molybdenum bronze (H x Preparation of MoO3

[0057] Step 1: Add 200 mg of α-MoO3 to 6 mL of an aqueous solution containing hydrochloric acid (V(HCl):V(H2O) = 9:1), and add 100 mg of aluminum foil in several batches while stirring at room temperature. After the reaction is complete, centrifuge, wash, and vacuum dry to obtain hydrogen molybdenum bronze (H2O). x MoO3 nanoparticles.

[0058] Step 2: Add 100 mg H xMoO3 was dispersed in 30 mL of ultrapure water and sonicated for 4 hours using a cell disruptor with the following parameters: power 390 W, frequency 20 kHz, sonication time 5 s, interval 5 s, and total time 4 h. H2 was removed by centrifugation. x MoO3 nanomaterials, supernatant lyophilized to obtain ultrasmall H x MoO3.

[0059] Example 8 Ultra-small hydrogen-molybdenum bronze (H x Preparation of MoO3

[0060] Step 1: Add 200 mg of h-MoO3 to 6 mL of an aqueous solution containing sulfuric acid (V(H2SO4):V(H2O) = 1:2), and add 100 mg of aluminum foil in multiple batches while stirring at room temperature. After the reaction is complete, centrifuge, wash, and vacuum dry to obtain hydrogen molybdenum bronze (H2SO4). x MoO3 nanoparticles.

[0061] Step 2: Add 100 mg H x MoO3 was dispersed in 30 mL of ultrapure water and sonicated for 4 hours using a cell disruptor with the following parameters: power 390 W, frequency 20 kHz, sonication time 5 s, interval 5 s, and total time 4 h. H2 was removed by centrifugation. x MoO3 nanomaterials, supernatant lyophilized to obtain ultrasmall H x MoO3.

[0062] Example 9 Ultra-small hydrogen-molybdenum bronze (H x Preparation of MoO3

[0063] Step 1: Add 200 mg of α-MoO3 to 6 mL of an aqueous solution containing sulfuric acid (V(H2SO4):V(H2O) = 2:1), and add 1000 mg of aluminum powder in multiple batches while stirring at 0°C. After the reaction is complete, centrifuge, wash, and vacuum dry to obtain hydrogen molybdenum bronze (H). x MoO3 nanoparticles.

[0064] Step 2: Add 100 mg H x MoO3 was dispersed in 30 mL of ultrapure water and sonicated for 4 hours using a cell disruptor with the following parameters: power 390 W, frequency 20 kHz, sonication time 5 s, interval 5 s, and total time 4 h. H2 was removed by centrifugation. x MoO3 nanomaterials, supernatant lyophilized to obtain ultrasmall H x MoO3.

[0065] Example 10 Ultra-small hydrogen-molybdenum bronze (H x Preparation of MoO3

[0066] Step 1: Add 200 mg of α-MoO3 to 6 mL of an aqueous solution containing nitric acid (V(HNO3):V(H2O) = 1:9), and add 100 mg of aluminum foil in multiple batches while stirring at room temperature. After the reaction is complete, centrifuge, wash, and vacuum dry to obtain hydrogen molybdenum bronze (H). x MoO3 nanoparticles.

[0067] Step 2: Add 100 mg H x MoO3 was dispersed in 30 mL of ultrapure water and sonicated for 4 hours using a cell disruptor with the following parameters: power 390 W, frequency 20 kHz, sonication time 5 s, interval 5 s, and total time 4 h. H2 was removed by centrifugation. x MoO3 nanomaterials, supernatant lyophilized to obtain ultrasmall H x MoO3.

[0068] Example 11 Ultra-small hydrogen-molybdenum bronze (H x Preparation of MoO3

[0069] Step 1: Add 200 mg of α-MoO3 to 6 mL of an aqueous solution containing nitric acid (V(HNO3):V(H2O) = 9:1), and add 20 mg of aluminum foil in several batches while stirring at room temperature. After the reaction is complete, centrifuge, wash, and vacuum dry to obtain hydrogen molybdenum bronze (H). x MoO3 nanoparticles.

[0070] Step 2: Add 100 mg H x MoO3 was dispersed in 30 mL of ultrapure water and sonicated for 4 hours using a cell disruptor with the following parameters: power 390 W, frequency 20 kHz, sonication time 5 s, interval 5 s, and total time 4 h. H2 was removed by centrifugation. x MoO3 nanomaterials, supernatant lyophilized to obtain ultrasmall H x MoO3.

[0071] Example 12 Ultra-small hydrogen-molybdenum bronze (H x Preparation of MoO3

[0072] Step 1: Add 200 mg of h-MoO3 to 6 mL of an aqueous solution containing nitric acid (V(HNO3):V(H2O) = 5:1), and add 100 mg of aluminum powder in multiple batches while stirring at 60°C. After the reaction is complete, centrifuge, wash, and vacuum dry to obtain hydrogen molybdenum bronze (H). x MoO3 nanoparticles.

[0073] Step 2: Add 100 mg H xMoO3 was dispersed in 30 mL of ultrapure water and sonicated for 4 hours using a cell disruptor with the following parameters: power 390 W, frequency 20 kHz, sonication time 5 s, interval 5 s, and total time 4 h. H2 was removed by centrifugation. x MoO3 nanomaterials, supernatant lyophilized to obtain ultrasmall H x MoO3.

[0074] Example 13 Ultra-small hydrogen-molybdenum bronze (H x Preparation of MoO3

[0075] Step 1: Add 200 mg of α-MoO3 to 6 mL of an aqueous solution containing acetic acid (V(CH3COOH):V(H2O) = 1:1), and add 200 mg of aluminum powder in several batches while stirring at room temperature. After the reaction is complete, centrifuge, wash, and vacuum dry to obtain hydrogen molybdenum bronze (H). x MoO3 nanoparticles.

[0076] Step 2: Add 100 mg H x MoO3 was dispersed in 30 mL of ultrapure water and sonicated for 4 hours using a cell disruptor with the following parameters: power 390 W, frequency 20 kHz, sonication time 5 s, interval 5 s, and total time 4 h. H2 was removed by centrifugation. x MoO3 nanomaterials, supernatant lyophilized to obtain ultrasmall H x MoO3.

[0077] Example 14 Ultra-small hydrogen-molybdenum bronze (H x Preparation of MoO3

[0078] Step 1: Add 200 mg h-MoO3 to 6 mL of an aqueous solution containing acetic acid (V(CH3COOH):V(H2O) = 2:1), and add 100 mg of aluminum foil in multiple batches while stirring at room temperature. After the reaction is complete, centrifuge, wash, and vacuum dry to obtain hydrogen molybdenum bronze (H). x MoO3 nanoparticles.

[0079] Step 2: Add 100 mg H x MoO3 was dispersed in 30 mL of ultrapure water and sonicated for 4 hours using a cell disruptor with the following parameters: power 390 W, frequency 20 kHz, sonication time 5 s, interval 5 s, and total time 4 h. H2 was removed by centrifugation. x MoO3 nanomaterials, supernatant lyophilized to obtain ultrasmall H x MoO3.

[0080] Example 15 Ultra-small hydrogen-molybdenum bronze (H x Transmission electron microscopy characterization of MoO3

[0081] The ultra-small H in Example 1 x MoO3 was characterized by transmission electron microscopy (TEM) using existing methods, and the results are shown in the attached figure. Figure 1 As shown. The obtained ultra-small H x MoO3 has a regular morphology and uniform distribution. Statistical particle size analysis shows that this H... x The average particle size of MoO3 is 3.2 ± 0.1 nm.

[0082] Example 16 Ultra-small hydrogen-molybdenum bronze (H x X-ray powder diffraction characterization of MoO3

[0083] The ultrasmall H prepared in Example 1 x MoO3 was characterized by X-ray powder diffraction (XRD), and the results are shown in the attached figure. Figure 2 As shown. After hydrogenation treatment, its diffraction peaks are similar to those of hydrogen-doped molybdenum oxide (H₂O). 1.68 MoO3, PDF#35-0604; H 0.93 The standard diffraction peaks of MoO3 (PDF#36-0605) show good agreement. Notably, the diffraction peaks corresponding to the MoO3 (020) crystal plane show a slight positive shift and split into two peaks after hydrogenation, which is attributed to lattice expansion caused by hydrogen insertion.

[0084] Example 17 Ultra-small hydrogen-molybdenum bronze (H x RONS removal performance of MoO3

[0085] The ultrasmall H prepared in Example 1 x The performance of MoO3 in RONS removal was evaluated, and the results are attached. Figure 3 As shown. Ultra-small H x MoO3 exhibits superior and sustained reducing properties, effectively scavenging ·OH, H2O2, and ·O2. ¯ and ONOO ¯ Reactive oxygen species (RONS).

[0086] Example 18 Ultra-small H x Cellular safety of MoO3 nanomaterials

[0087] The ultrasmall H prepared in Example 1 x Cellular safety evaluation of MoO3 was performed, and the results are attached. Figure 4 As shown. Cell viability was assessed using the CCK-8 assay, revealing that ultrasmall H cells... x MoO3 exhibits excellent biocompatibility in renal tubular epithelial cells (NRK-52E), with cell survival exceeding 90% even at high concentrations.

[0088] Example 19 Ultra-small H x Therapeutic properties of MoO3 nanomaterials against cisplatin-damaged cells

[0089] Evaluation of ultra-small H using the CCK-8 method x The protective effect of MoO3 on cisplatin-damaged NRK-52E cells. (See attached image) Figure 5 As shown, dose gradient experiments confirmed that the material can significantly alleviate renal tubular epithelial cell toxicity, and exhibits the maximum protective performance at a concentration of 16 µg / mL, i.e., the cell survival rate is increased to 105.3%.

[0090] Example 20 Ultra-small H x The ability of MoO3 nanomaterials to scavenge RONS in cisplatin-damaged cells

[0091] The ultrasmall H prepared in Example 1 x MoO3 was used to evaluate the level of RONS in DPP-damaged cells, and the results are shown in the attached figure. Figure 6 As shown, intracellular RONS levels, indicated by green fluorescence, significantly increased after DPP damage. In contrast, ultrasmall H... x The fluorescence signal in the MoO3-treated group was significantly reduced and approached the level of the control group, indicating that it can effectively clear RONS overexpressed in cells.

[0092] Example 21 Ultra-small H x DNA protection properties of MoO3 nanomaterials in cisplatin-damaged cells

[0093] The ultrasmall H prepared in Example 1 x The DNA protective effect of MoO3 on DPP-damaged cells was evaluated, and the results are attached. Figure 7 As shown. γ-H2AX immunofluorescence staining results confirmed that ultrasmall H... x MoO3 can significantly reduce DNA damage.

[0094] Example 22 Ultra-small H x Biosafety of MoO3 Nanomaterials

[0095] The ultrasmall H prepared in Example 1 x The biocompatibility of MoO3 was evaluated using a zebrafish model, and the results are attached. Figure 7 As shown in the figure, the survival rate remained high in all exposure groups, with no significant decrease even at the highest concentration, indicating that ultra-small H+... x MoO3 exhibits good biocompatibility.

Claims

1. An ultra-small H x MoO3 nanomaterials, characterized by: The average particle size of the nanoparticles is ≤ 10 nm, and x = 0.01 ~ 2.

58.

2. The ultra-small H according to claim 1 x Preparation method of MoO3 nanomaterials: Molybdenum trioxide is dispersed in an acidic solution containing hydrogen protons, and elemental aluminum is added as a reducing agent to carry out a reduction intercalation reaction. After the reaction, the material is purified by centrifugation, washed, and vacuum dried to obtain H2O3 nanomaterials. x MoO3 nanoparticles; the resulting H x MoO3 nanoparticles were dispersed in an aqueous medium, ultrasonically broken down, and then separated by ultracentrifugation to obtain H nanoparticles with an average particle size ≤ 10 nm. x MoO3 nanoparticles.

3. The preparation method according to claim 2, wherein molybdenum trioxide is selected from: α-MoO 3、 Any one or more of h-MoO3.

4. The preparation method according to claim 2, characterized in that... The acidic solution containing hydrogen protons is selected from any one or more of hydrochloric acid, sulfuric acid, nitric acid, trifluoroacetic acid, acetic acid, and hydrofluoric acid; wherein the volume ratio of acid to water is 1:9 to 9:

1.

5. The preparation method according to claim 2, characterized in that... The elemental aluminum is selected from any one or more of aluminum foil and aluminum powder; the mass ratio of elemental aluminum to MoO3 is (0.1-5):

1.

6. The preparation method according to claim 2, characterized in that: The aluminum foil has a thickness of 0.01 ~ 0.5 mm and the aluminum powder has a particle size of 100 nm ~ 100 µm.

7. The preparation method according to claim 2, characterized in that... The temperature for the reduction intercalation reaction is 0 ~ 60°C, and the reaction time is 0.5 ~ 48 hours.

8. The preparation method according to claim 2, wherein the device used for ultrasonic disruption is a controllable ultrasonic disruptor, and the disruption medium for ultrasonic disruption is selected from any one or more of deionized water and phosphate buffer solution with pH 7.0 to 7.

4.

9. The preparation method according to claim 8, wherein the controllable ultrasonic breaker is a probe-type breaker; the power is 100-800W, the frequency is 20-40 kHz, the ultrasonic breaker adopts pulse mode, the on / off time ratio is 1:1-1:4, and the time is 0.5-12 hours.

10. The ultra-small H according to claim 1 x Application of MoO3 nanomaterials in the preparation of drugs for the treatment, prevention, and detection of tumors.

11. The ultra-small H as described in claim 1 x Application of MoO3 nanomaterials in the preparation of drugs for the treatment, prevention, and detection of inflammatory bowel disease.

12. The ultra-small H according to claim 2 x Application of MoO3 nanomaterials in the preparation of drugs for the treatment, prevention, and detection of kidney damage.

13. The application of claim 12, wherein the kidney injury is acute kidney injury.

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