Gold-palladium-nitrogen-doped carbon ribbon modified g-C3N4 nanosheet as well as preparation method and application thereof

Abstract

The invention discloses a g-C3N4 nanosheet modified by a gold-palladium-nitrogen doped carbon ribbon as well as a preparation method and application of the g-C3N4 nanosheet. The preparation method comprises the following steps: doping UFR-NC into g-C3N4 to form a g-C3N4 / UFR-NC composite nanomaterial; the g-C3N4 / UFR-NC composite nanomaterial is used as a carrier, and gold-palladium core-shell particles are loaded on the g-C3N4 / UFR-NC composite nanomaterial, so that the g-C3N4 nanosheet modified by the gold-palladium-nitrogen doped carbon ribbon is obtained. The g-C3N4 nanosheet modified by the gold-doped palladium-nitrogen-doped carbon ribbons, disclosed by the invention, has multiple enzyme-like activities and good photocatalytic hydrogen production and hydrogen storage and release performance; meanwhile, under the enhancement effect of 808 nm near-infrared light illumination, the multi-enzyme activity is achieved, and the hydrogen storage and release performance is high. The traditional Chinese medicine composition can reduce oxidative stress injury in vivo and inhibit neuroinflammation, and has an obvious treatment effect on microglia mediated neuroinflammatory encephalopathy such as Parkinson's disease, Alzheimer's disease, cerebral trauma and cerebral apoplexy.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of biological medicine, and particularly relates to a gold@palladium-nitrogen-doped carbon ribbon modified g-C3N4 nanosheet, a preparation method and application thereof, and specifically relates to application of the gold@palladium-nitrogen-doped carbon ribbon modified g-C3N4 nanosheet in a drug for synergistically enhancing treatment of Parkinson's disease, Alzheimer's disease, brain trauma, stroke and other microglia-mediated neuroinflammatory encephalopathy under near-infrared light irradiation. BACKGROUND

[0002] The existing therapies for Parkinson's disease, Alzheimer's disease, brain trauma and stroke and other neuroinflammatory diseases mainly focus on symptom relief (such as dopamine replacement therapy, cholinesterase inhibitors), but have limitations such as poor blood-brain barrier penetration, obvious side effects of long-term medication, and inability to reverse the neurodegenerative process. Oxidative stress and neuroinflammation are the core pathological mechanisms of these diseases: oxidative stress leads to oxidative damage of neuronal proteins / lipids through excessive generation of reactive oxygen species (ROS), promotes Aβ plaque, alpha-synuclein aggregation and mitochondrial dysfunction; neuroinflammation is driven by abnormal activation of microglia, releasing TNF-α, IL-1β and other pro-inflammatory factors, exacerbating neurotoxicity and forming a vicious cycle with oxidative stress. Therefore, developing multifunctional antioxidants that can efficiently scavenge ROS, inhibit lipid peroxidation, penetrate the blood-brain barrier for targeted delivery, reduce neuronal apoptosis and inhibit microglial overactivation, thereby breaking the neuroinflammation-oxidative stress positive feedback loop, reducing ischemia-reperfusion injury and delaying neurodegeneration, has become a promising treatment strategy for Parkinson's disease, Alzheimer's disease, brain trauma and stroke and other neuroinflammatory diseases. Hydrogen (H2) is a selective antioxidant gas, and H2 therapy has been less studied in brain diseases and its mechanism is unclear, so further exploring the medical application of H2 therapy in brain diseases is of great significance. Although H2 therapy has many advantages, it has problems such as small molecules, easy diffusion and low solubility in water. With the rapid development of nanotechnology in the field of biomedicine, nanomaterials have also received extensive attention in H2 therapy. PdNPs have good hydrogen storage and release performance, but hydrogen needs to be stored before being released, so the amount of hydrogen released by both is limited, and the amount of ROS scavenged is also limited, and the treatment effect may not meet expectations. Therefore, how to increase the amount of hydrogen and enhance the antioxidant capacity of nanomaterials when they reach the lesion site so as to more efficiently and completely scavenge ROS has become a very challenging problem. SUMMARY

[0003] The technical problem solved by the present application is to overcome the deficiencies in the prior art and provide a gold@palladium-nitrogen-doped carbon ribbon modified g-C3N4 nanosheet, a preparation method and application thereof.The gold@palladium-nitrogen-doped carbon ribbon modified g-C3N4 nanosheet prepared by the present application is a g-C3N4 / UFR-NC / Au@Pd composite nanomaterial with a gold-palladium core-shell loaded nitrogen-doped carbon ribbon.The gold@palladium-nitrogen-doped carbon ribbon modified g-C3N4 nanosheet has multiple enzyme-like activities, good photocatalytic hydrogen production and hydrogen storage and release performance.Meanwhile, under the enhancement of 808 nm near-infrared light, the g-C3N4 / UFR-NC / Au@Pd composite nanomaterial with high hydrogen storage and release performance can reduce oxidative stress damage and inhibit neuroinflammation, thereby achieving the protection of neurons and providing a new idea for the treatment of neuroinflammatory diseases such as Parkinson's disease, Alzheimer's disease, brain trauma and stroke.

[0004] To solve the above technical problems, the present application provides a gold@palladium-nitrogen-doped carbon ribbon modified g-C3N4 nanosheet (also known as gold@palladium-carbon nitride nanoscale enzyme), which dopes UFR-NC in g-C3N4 to form a g-C3N4 / UFR-NC composite nanomaterial; and gold-palladium core-shell particles are loaded on the g-C3N4 / UFR-NC composite nanomaterial using the g-C3N4 / UFR-NC composite nanomaterial as a carrier.The gold@palladium-nitrogen-doped carbon ribbon modified g-C3N4 nanosheet further comprises gold as the core and palladium as the shell of the gold-palladium core-shell particles.The gold@palladium-nitrogen-doped carbon ribbon modified g-C3N4 nanosheet further comprises gold as the core and palladium as the shell of the gold-palladium core-shell particles.The diameter of the gold-palladium core-shell particles is 20-30 nm.Based on a general technical concept, the present application further provides a preparation method of the gold@palladium-nitrogen-doped carbon ribbon modified g-C3N4 nanosheet, which comprises the following steps: S1, preparing nitrogen-doped carbon ribbon modified graphite phase carbon nitride; S2, dissolving the nitrogen-doped carbon ribbon modified graphite phase carbon nitride in water, adding a sodium citrate solution, gold chloride trihydrate and Na2PdCl4, and stirring to obtain a gold@palladium-nitrogen-doped carbon ribbon modified g-C3N4 nanosheet. l4The solution is stirred and mixed, ascorbic acid is added for reaction, and drying is performed to obtain gold@palladium-nitrogen-doped carbon ribbon modified g-C3N4 nanosheets. According to the preparation method, further, the S1 includes the following steps: S1-1, urea is placed in a crucible and heated and kept in an oil bath to obtain a transparent melted urea solution; S1-2, UFR is added to the urea solution to form a uniform solution, and condensation is performed to obtain a solid powder; S1-3, the solid powder is calcined in a tube furnace at a temperature increasing rate of 5 ℃ / min and at 600 ℃ for 3 h to obtain nitrogen-doped carbon ribbon modified graphite phase carbon nitride. According to the preparation method, further, the S2 includes the following steps: S2-1, after PdCl2 and NaCl are dissolved, heating is performed to 90 ℃, stirring is performed for reaction for 30 min, and Na2PdCl4 solution is obtained; S2-2, the nitrogen-doped carbon ribbon modified graphite phase carbon nitride is dissolved in water, a sodium citrate solution, gold trichloride hydrate and Na2PdCl4 solution are added, and stirring and mixing are performed to obtain a reaction system; S2-3, ascorbic acid is dissolved in water, is added to the reaction system at a speed of 2 mL / h by using a syringe pump for reaction, and drying is performed after centrifugation and removal of supernatant of the reaction solution to obtain gold@palladium-nitrogen-doped carbon ribbon modified g-C3N4 nanosheets. l4 solution; S2-2, the nitrogen-doped carbon ribbon modified graphite phase carbon nitride is dissolved in water, a sodium citrate solution, gold trichloride hydrate and Na2PdCl4 solution are added, and stirring and mixing are performed to obtain a reaction system; S2-3, ascorbic acid is dissolved in water, is added to the reaction system at a speed of 2 mL / h by using a syringe pump for reaction, and drying is performed after centrifugation and removal of supernatant of the reaction solution to obtain gold@palladium-nitrogen-doped carbon ribbon modified g-C3N4 nanosheets. l4 solution; S2-2, the nitrogen-doped carbon ribbon modified graphite phase carbon nitride is dissolved in water, a sodium citrate solution, gold trichloride hydrate and Na2PdCl4 solution are added, and stirring and mixing are performed to obtain a reaction system; S2-3, ascorbic acid is dissolved in water, is added to the reaction system at a speed of 2 mL / h by using a syringe pump for reaction, and drying is performed after centrifugation and removal of supernatant of the reaction solution to obtain gold@palladium-nitrogen-doped carbon ribbon modified g-C3N4 nanosheets. Based on a general technical concept, the application further provides application of the gold@palladium-nitrogen-doped carbon ribbon modified g-C3N4 nanosheets in preparation of a drug for protecting neurons. Based on a general technical concept, the application further provides application of the gold@palladium-nitrogen-doped carbon ribbon modified g-C3N4 nanosheets in preparation of a drug for treating neuroinflammatory diseases such as Parkinson's disease, Alzheimer's disease, brain trauma and stroke. The application further provides application of the gold@palladium-nitrogen-doped carbon ribbon modified g-C3N4 nanosheets in preparation of a drug for inhibiting neuroinflammation. The application further provides application of the gold@palladium-nitrogen-doped carbon ribbon modified g-C3N4 nanosheets in preparation of a drug for reducing oxidative stress damage in vivo.

[0005] Compared with the prior art, the advantages of the present application are that (1) the present application provides a gold@palladium-nitrogen-doped carbon ribbon modified g-C3N4 nanosheet, which has multiple antioxidant enzyme activities, first, can scavenge ROS, reduce the level of oxidative stress and inflammation; second, greatly improves the hydrogen release capacity and photocatalytic hydrogen production performance of g-C3N4 / UFR-NC / Au@Pd under the enhancement of near-infrared light, studies have shown that hydrogen has an antioxidant stress effect, which can efficiently scavenge ROS, thereby reducing the level of oxidative stress and inflammation in the body; third, g-C3N4 / UFR-NC / Au@Pd can efficiently penetrate the BBB, and can achieve non-invasive drug delivery and ultimately reach the midbrain for treatment through nasal administration. Based on the above multiple effects, the in vivo oxidative stress level is ultimately regulated, neuronal apoptosis is inhibited, the inflammatory microenvironment is improved, the function of protecting neurons is achieved, and further treatment of 6-OHDA-induced Parkinson's disease (PD) mouse models is achieved through nasal administration. As can be seen from the above, the g-C3N4 / UFR-NC / Au@Pd with multiple antioxidant enzyme activities and hydrogen storage and release performance combined with hydrogen-light-heat can efficiently scavenge ROS, reduce oxidative stress, reduce neuronal apoptosis, improve the inflammatory microenvironment, and achieve the purpose of treating Parkinson's disease, providing a more promising new treatment strategy for the clinical treatment of Parkinson's disease, Alzheimer's disease, brain trauma and stroke and other brain diseases, and also embodying the longer-term development of nanomedicine in the field of nervous system diseases.

[0006] (2) The present application provides a gold@palladium-nitrogen-doped carbon ribbon modified g-C3N4 nanosheet, g-C3N4 has a strong photocatalytic hydrogen production capacity, but the band gap of g-C3N4 is about 2.7 eV, which can only absorb and utilize visible light with a wavelength of less than 460 nm. In order to improve the photocatalytic effect of g-C3N4 and expand its application range, the present application uses g-C3N4 / UFR-NC composite material, which has excellent optical absorption performance for visible light and near-infrared light, and the band gap can be easily adjusted by changing the content of UFR-NC band. The g-C3N4 / UFR-NC nanosheet can exhibit more advantages than the pure g-C3N4 nanosheet: first, after doping of nitrogen and carbon, two non-metallic elements, the light absorption range of the g-C3N4 nanosheet is greatly widened, the g-C3N4 nanosheet modified by nitrogen-doped carbon band can absorb near-infrared light, and activate g-C3N4 photocatalytic water splitting to release hydrogen under near-infrared light stimulation; second, the larger specific surface area, better crystallinity and excellent stability provide more active sites for loading gold palladium nanocore-shell structure. BRIEF DESCRIPTION OF DRAWINGS

[0007] In order to make the purposes, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the drawings in the embodiments of the present application. Figure 1 HRTEM detection results of Example 1. Figure 2 XPS characterization chart of g-C3N4 and g-C3N4 / UFR-NC. Figure 3 XPS characterization chart of g-C3N4 / UFR-NC / Au@Pd. Figure 4 XRD characterization chart of g-C3N4, g-C3N4 / UFR-NC and g-C3N4 / UFR-NC / Au@Pd. Figure 5 PL spectrum chart of g-C3N4 / UFR-NC / Au@Pd and RhB@g-C3N4 / UFR-NC / Au@Pd. Figure 6 SOD-like enzyme activity detection results of g-C3N4 / UFR-NC and g-C3N4 / UFR-NC / Au@Pd composite nanomaterials. Figure 7 POD-like enzyme activity detection results of g-C3N4 / UFR-NC and g-C3N4 / UFR-NC / Au@Pd composite nanomaterials. Figure 8 CAT-like enzyme activity detection results of g-C3N4 / UFR-NC and g-C3N4 / UFR-NC / Au@Pd composite nanomaterials. Figure 9 GPx-like enzyme activity detection results of g-C3N4 / UFR-NC and g-C3N4 / UFR-NC / Au@Pd composite nanomaterials. Figure 10 Photocatalytic hydrogen production performance detection results of g-C3N4, g-C3N4 / UFR-NC and g-C3N4 / UFR-NC / Au@Pd composite nanomaterials. Figure 11 In-vitro hydrogen release ability detection results of g-C3N4 / UFR-NC / Au@Pd under near-infrared laser irradiation or not after hydrogen outflow. Figure 12 Extinction coefficient detection results of g-C3N4 / UFR-NC, g-C3N4 / UFR-NC / Au@Pd and g-C3N4 / UFR-NC / Au@Pd+H2 composite nanomaterials. Figure 13 In-vitro photothermal performance detection results of g-C3N4 / UFR-NC, g-C3N4 / UFR-NC / Au@Pd and g-C3N4 / UFR-NC / Au@Pd+H2 composite nanomaterials. Figure 14 MTT method exploration results. Figure 15 Calcein-AM / PI staining results of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials on damaged neurons. Figure 16Calcein-AM / PI staining results of damaged neurons treated by g-C3N4 / UFR-NC / Au@Pd composite nanomaterial combined with hydrogen-gas-photothermal. Figure 17 ROS staining results of damaged neurons treated by g-C3N4 / UFR-NC / Au@Pd composite nanomaterial combined with hydrogen-gas-photothermal. Figure 18 iNOS / Arg1 mRNA expression level detection results of 6-OHDA-induced BV2 cells treated by g-C3N4 / UFR-NC / Au@Pd composite nanomaterial combined with hydrogen-gas-photothermal. Figure 19 Detection results of pro-inflammatory factors IL-1β, IL-6, TNF-α secreted by 6-OHDA-induced BV2 cells treated by g-C3N4 / UFR-NC / Au@Pd composite nanomaterial combined with hydrogen-gas-photothermal. Figure 20 In vivo fluorescence imaging detection results of mice intranasally administered with RhB@g-C3N4 / UFR-NC / Au@Pd composite nanomaterial at different times. Figure 21 Animal behavior experiment results of PD mice treated by g-C3N4 / UFR-NC / Au@Pd composite nanomaterial combined with hydrogen-gas-photothermal. Figure 22 Western blotting experiment results of PD mice treated by g-C3N4 / UFR-NC / Au@Pd composite nanomaterial combined with hydrogen-gas-photothermal. DETAILED DESCRIPTION

[0008] Example 1: A gold@palladium-nitrogen-doped carbon ribbon modified g-C3N4 nanosheet according to the present application.

[0009] The preparation method comprises the following steps: (1) preparing nitrogen-doped carbon ribbon modified graphite phase carbon nitride (g-C3N4 / UFR-NC). 1.1, 20 g of urea is placed in a crucible, heated at 150°C, and kept in an oil bath for 20 min to obtain a transparent melted urea solution. 1.2, Then 0.02 g of UFR is added to form a uniform solution and cooled to room temperature. The solid powder formed after condensation is calcined in a tube furnace at a temperature increasing rate of 5°C / min for 3 h at 600°C. After cooling to room temperature, the prepared solid powder is marked as g-C3N4 / UFR-NC.

[0010] (2) Preparation of gold-palladium core-shell loaded nitrogen-doped carbon ribbon modified graphite phase carbon nitride (g-C3N4 / UFR-NC / Au@Pd). 2.1, weigh 86.4 mg of PdCl2 and 60 mg of NaCl and dissolve in 10 mL of ultrapure water, heat to 90°C and stir for 30 min to obtain Na2PdCl4 solution. 2.2, 0.2 g of g-C3N4 / UFR-NC is added to the Na2PdCl4 solution and stirred for 30 min to obtain a uniform solution. 2.3, 0.2 g of NaAuCl4 is added to the solution and stirred for 30 min to obtain a uniform solution. 2.4, The solution is cooled to room temperature and the solid powder formed after condensation is marked as g-C3N4 / UFR-NC / Au@Pd. l4Solution. 2.2, 5 mg of g-C3N4 / UFR-NC solid powder prepared in the previous step was weighed and dissolved in 40 mL of ultrapure water. Then sodium citrate solution, gold chloride trihydrate and Na2PdCl4 solution were added respectively, and the reaction system was stirred at room temperature. 2.3, Finally, 18 mg of ascorbic acid was weighed and dissolved in 10 mL of ultrapure water, and was added into the reaction system at a speed of 2 mL / h by using a syringe pump. After the reaction was completed, the supernatant was discarded by centrifugation, washed with ultrapure water three times, 75% alcohol twice, and finally anhydrous ethanol once, and the obtained gray-black solid was dried and labeled as g-C3N4 / UFR-NC / Au@Pd. The preparation method of pure graphite phase carbon nitride (g-C3N4) is as follows: 20 g of urea was weighed and placed in a tube furnace, and the temperature was raised to 600℃ at a rate of 5℃ / min, and calcined for 3h. After cooling to room temperature, the prepared solid powder was labeled as g-C3N4. l4 Solution. 2.2, 5 mg of g-C3N4 / UFR-NC solid powder prepared in the previous step was weighed and dissolved in 40 mL of ultrapure water. Then sodium citrate solution, gold chloride trihydrate and Na2PdCl4 solution were added respectively, and the reaction system was stirred at room temperature. 2.3, Finally, 18 mg of ascorbic acid was weighed and dissolved in 10 mL of ultrapure water, and was added into the reaction system at a speed of 2 mL / h by using a syringe pump. After the reaction was completed, the supernatant was discarded by centrifugation, washed with ultrapure water three times, 75% alcohol twice, and finally anhydrous ethanol once, and the obtained gray-black solid was dried and labeled as g-C3N4 / UFR-NC / Au@Pd. The preparation method of pure graphite phase carbon nitride (g-C3N4) is as follows: 20 g of urea was weighed and placed in a tube furnace, and the temperature was raised to 600℃ at a rate of 5℃ / min, and calcined for 3h. After cooling to room temperature, the prepared solid powder was labeled as g-C3N4.

[0011] Experiment 1: Characterization of g-C3N4 / UFR-NC / Au@Pd composite material.

[0012] 1. High-resolution transmission electron microscopy (HRTEM) detection: Figure 1 The HRTEM detection results are shown in the figure, where A is the HRTEM image of g-C3N4 / UFR-NC, and the scale = 200 nm. B is the TEM image of g-C3N4 / UFR-NC, and the scale = 100 nm. C is the HRTEM image of g-C3N4 / UFR-NC / Au@Pd, and the scale = 200 nm. D is the HRTEM image of g-C3N4 / UFR-NC / Au@Pd, and the scale = 10 nm. From A and B in the figure, it can be seen that g-C3N4 / UFR-NC is a thin layer, large specific surface area, irregular edge nanosheet, and the surface is decorated with black thin silk belts. From C in the figure, it can be seen that a large number of gold-palladium core-shell nanoparticles are uniformly distributed on the g-C3N4 / UFR-NC composite nanomaterial. From D in the figure, it can be seen that the gold-palladium core-shell loaded on the g-C3N4 / UFR-NC composite nanomaterial has a size of about 20-30 nm, and the gold nanoparticles as the core have a size of about 5 nm, which preliminarily proves the successful synthesis of g-C3N4 / UFR-NC / Au@Pd composite nanomaterial.

[0013] 2. X-ray photoelectron spectroscopy (XPS) detection: Figure 2XPS characterization chart of g-C3N4 and g-C3N4 / UFR-NC. A in the chart is the XPS full spectrum of g-C3N4 and g-C3N4 / UFR-NC; B, C, D in the chart are the XPS fine spectrum of C 1s, N 1s, O 1s of g-C3N4 and g-C3N4 / UFR-NC respectively. It can be seen from the chart that: g-C3N4 and g-C3N4 / UFR-NC both contain special peaks of C 1s, N 1s and O 1s, the C atomic ratio of g-C3N4 / UFR-NC is obviously higher than that of g-C3N4, the peak area ratio of the characteristic peaks of g-C3N4 and g-C3N4 / UFR-NC at 287.78 eV and 284.61 eV is 7.54 and 1.59 respectively, and the above results show the successful preparation of g-C3N4 / UFR-NC.

[0014] Figure 3 XPS characterization chart of g-C3N4 / UFR-NC / Au@Pd; A in the chart is the XPS full spectrum of g-C3N4 / UFR-NC / Au@Pd; B, C, D, E, F in the chart are the XPS fine spectrum of C 1s, N 1s, O 1s, Pd 3d, Au 4f of g-C3N4 / UFR-NC / Au@Pd respectively. From the XPS full spectrum and each fine spectrum of g-C3N4 / UFR-NC / Au@Pd, the peaks of C, N, O, Pd and Au five elements can be observed, and the Pd element is at and two places respectively corresponding to Pd 3d3 and Pd 3d5 two absorption peaks, and the Au element is at and two places respectively corresponding to Au 4f5 and Au 4f7 two absorption peaks. The above results are compared with Figure 2 the XPS spectrum of g-C3N4 / UFR-NC, it can be seen that the two elements of Au and Pd are obviously increased in g-C3N4 / UFR-NC / Au@Pd composite nanomaterial, which shows that the gold and palladium core-shell nanoparticles are successfully loaded on g-C3N4 / UFR-NC, that is, the successful synthesis of g-C3N4 / UFR-NC / Au@Pd.

[0015] 3. X-ray diffraction (XRD) detection: Figure 4XRD characterization chart of g-C3N4, g-C3N4 / UFR-NC and g-C3N4 / UFR-NC / Au@Pd. The results show that g-C3N4, g-C3N4 / UFR-NC and g-C3N4 / UFR-NC / Au@Pd all have diffraction peaks at 2θ values of about 13.0° and 27.6°, corresponding to the (100) and (002) crystal planes of g-C3N4, respectively; the characteristic peak intensity of g-C3N4 / UFR-NC at the (002) crystal plane is significantly higher than that of g-C3N4, indicating that the modification of UFR-NC on g-C3N4 improves the crystallinity of g-C3N4 / UFR-NC; the XRD results of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials show five characteristic peaks of metal Au and Pd, indicating that the gold-palladium core-shell nanoparticles have been successfully loaded on g-C3N4 / UFR-NC composite nanomaterials, i.e. the successful synthesis of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials.

[0016] 4. Fluorescence spectrum (PL) detection: Figure 5 PL spectrum of g-C3N4 / UFR-NC / Au@Pd and RhB@g-C3N4 / UFR-NC / Au@Pd; A in the figure is the PL spectrum of g-C3N4 / UFR-NC / Au@Pd; B in the figure is the PL spectrum of RhB@g-C3N4 / UFR-NC / Au@Pd. From the figure, it can be seen that g-C3N4 / UFR-NC / Au@Pd takes 368 nm as the excitation light wavelength, and the emission spectrum obtained has an emission peak at about 430 nm, proving that g-C3N4 / UFR-NC / Au@Pd has certain photoluminescence characteristics and emits blue fluorescence under ultraviolet light excitation. In order to facilitate further in vivo fluorescence imaging to judge the effect of nasal administration of the material into the brain, we test the fluorescence emission spectrum of the synthesized RhB@g-C3N4 / UFR-NC / Au@Pd. From B in the figure, it can be seen that RhB@g-C3N4 / UFR-NC / Au@Pd takes 532 nm as the excitation light wavelength, and the emission spectrum obtained has an emission peak at about 557 nm, indicating that RhB is successfully modified on the g-C3N4 / UFR-NC / Au@Pd composite nanomaterial.

[0017] Experiment two: detection of the enzyme-like activity of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials.

[0018] 1. SOD-like activity detection of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials: The SOD-like activity of g-C3N4 / UFR-NC and g-C3N4 / UFR-NC / Au@Pd composite nanomaterials was detected using an SOD activity detection kit (WST-8 method). Figure 6 Figure 1 shows the results of SOD-like activity detection of g-C3N4 / UFR-NC and g-C3N4 / UFR-NC / Au@Pd composite nanomaterials; A and B in the figure are the superoxide radical inhibition rate statistical chart (n>3) and SOD enzyme activity statistical chart (n>3) of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials at different concentrations (5 μg / mL, 15 μg / mL, 45 μg / mL and 90 μg / mL); C and D in the figure are the superoxide radical inhibition rate statistical chart (n>3) and SOD enzyme activity statistical chart (n>3) of g-C3N4 / UFR-NC and g-C3N4 / UFR-NC / Au@Pd composite nanomaterials at the same concentration (45 μg / mL). *p<0.05, **p<0.01, ***p<0.001, ****p<0.0001. As can be seen from A and B in the figure, the superoxide radical inhibition rate and SOD enzyme activity of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials increased in a concentration-dependent manner, indicating that g-C3N4 / UFR-NC / Au@Pd composite nanomaterials had strong SOD enzyme activity and could scavenge superoxide anion radicals. In addition, we detected the superoxide radical inhibition rate and SOD enzyme activity of g-C3N4 / UFR-NC and g-C3N4 / UFR-NC / Au@Pd composite nanomaterials, and the results can be seen from C and D in the figure. The superoxide radical inhibition rate and SOD enzyme activity of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials were about 8 times that of g-C3N4 / UFR-NC composite nanomaterials.

[0019] 2. POD-like activity detection of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials: Figure 7For the detection results of the POD-like enzyme activity of g-C3N4 / UFR-NC and g-C3N4 / UFR-NC / Au@Pd composite nanomaterials, A in the figure is an ultraviolet-spectroscopy diagram reflecting the POD-like enzyme activity of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials in different concentrations (5 μg / mL, 15 μg / mL, 45 μg / mL and 90 μg / mL); B in the figure is a curve diagram reflecting the absorbance change of the POD-like enzyme activity of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials within 20 min; C in the figure is an ultraviolet-spectroscopy diagram reflecting the POD-like enzyme activity of g-C3N4 / UFR-NC and g-C3N4 / UFR-NC / Au@Pd composite nanomaterials; D in the figure is the relative enzyme activity of the POD of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials under different pH (PH=2.5, 3.5, 4.5, 5.5, 7.4) conditions. As can be seen from A and B in the figure, under the condition of pH 4.5, the POD enzyme activity of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials increases with the increase of the concentration of the material. As can be seen from C in the figure, the POD enzyme activity of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials is obviously increased compared with that of g-C3N4 / UFR-NC composite nanomaterials. As can be seen from D in the figure, under the acidic condition, the POD enzyme activity of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials is higher, and reaches the highest at pH 4.5. Under the condition of pH 7.4, the relative enzyme activity of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials is as low as 19.77%. Therefore, g-C3N4 / UFR-NC / Au@Pd composite nanomaterials have strong POD enzyme activity under acidic or weakly acidic conditions, while under normal physiological conditions (pH=7.4), the POD enzyme activity of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials is weak, and the amount of ·OH generated is small, so it will not have obvious toxic effects on normal tissues and cells.

[0020] 3. Detection of the CAT-like enzyme activity of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials Figure 8For the results of the detection of the CAT-like enzyme activity of g-C3N4 / UFR-NC and g-C3N4 / UFR-NC / Au@Pd composite nanomaterials, Fig. A is a graph of the dissolved oxygen content of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials of different concentrations (5 μg / mL, 15 μg / mL, 45 μg / mL and 90 μg / mL); Fig. B is a digital photograph of the reaction solution after the addition of the same amount of H2O2 to g-C3N4 / UFR-NC / Au@Pd composite nanomaterials of different concentrations; Fig. C is a statistical graph of the CAT enzyme activity of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials of different concentrations (n>3); and Fig. D is a graph of the dissolved oxygen content of g-C3N4 / UFR-NC and g-C3N4 / UFR-NC / Au@Pd composite nanomaterials. ****p<0.0001. As can be seen from Fig. A, the dissolved oxygen content of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials increases with the increase of the concentration of the composite nanomaterials. As can be seen from the digital pictures in Fig. B, under the condition that other conditions remain unchanged, more and more bubbles are generated with the increase of the concentration of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials in the solution. The above results reflect that the CAT enzyme activity of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials has obvious concentration dependence. Similarly, in Fig. C, we verified this conclusion again through the detection results of the CAT enzyme activity detection kit. In Fig. D, by comparing the dissolved oxygen content of g-C3N4 / UFR-NC and g-C3N4 / UFR-NC / Au@Pd composite nanomaterials under the condition of the same concentration (45 μg / mL), the results show that the CAT enzyme activity of g-C3N4 / UFR-NC has been significantly improved after loading gold and palladium core-shell nanoparticles.

[0021] 4. Detection of the GPx-like enzyme activity of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials: The total GPx detection kit was used to detect the GPx-like enzyme activity of g-C3N4 / UFR-NC and g-C3N4 / UFR-NC / Au@Pd composite nanomaterials. Figure 9Figure 1 is the detection result of GPx enzyme activity of g-C3N4 / UFR-NC and g-C3N4 / UFR-NC / Au@Pd composite nanomaterials. A in the figure is a statistical chart of GPx enzyme activity of different concentrations of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials (n>3); B in the figure is a statistical chart of GPx enzyme activity of g-C3N4 / UFR-NC and g-C3N4 / UFR-NC / Au@Pd composite nanomaterials (n>3). ***p<0.001, ****p<0.0001. It can be seen from A in the figure that the GPx enzyme activity of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials gradually increases with the increase of concentration, and has obvious concentration dependence. It can be seen from B in the figure that the GPx enzyme activity of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials is obviously stronger than that of g-C3N4 / UFR-NC composite nanomaterials (p<0.001).

[0022] Experiment three: investigate the photocatalytic hydrogen production ability of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials.

[0023] Figure 10Figure 1 shows the results of photocatalytic hydrogen production performance testing of g-C3N4, g-C3N4 / UFR-NC, and g-C3N4 / UFR-NC / Au@Pd composite nanomaterials. Panels A, B, and C of the figure are graphs of H2 unit production (n=3), H2 total production (n=3), and H2 production rate (n=3) results for photocatalytic hydrogen production by g-C3N4, g-C3N4 / UFR-NC, and g-C3N4 / UFR-NC / Au@Pd composite nanomaterials within 4 h; panel D of the figure is a graph of the results of stability testing of photocatalytic hydrogen production by g-C3N4 / UFR-NC / Au@Pd composite nanomaterials after two cycles within 8 h. *p<0.05, ***p<0.001, ****p<0.0001. In panels A and B of the figure, by comparing the H2 unit production and H2 total production of g-C3N4, g-C3N4 / UFR-NC, and g-C3N4 / UFR-NC / Au@Pd composite nanomaterials within 4 h, it can be seen that both the H2 unit production and the H2 total production of g-C3N4 / UFR-NC composite nanomaterials are greater than those of g-C3N4, and that the H2 unit production and the H2 total production of g-C3N4 / UFR-NC composite nanomaterials after loading of gold and palladium core-shell are greater than those before loading. In addition, from panel C of the figure, it can be seen that the photocatalytic hydrogen production rates of g-C3N4, g-C3N4 / UFR-NC, and g-C3N4 / UFR-NC / Au@Pd composite nanomaterials are 96.3 μmol / h, 123.9 μmol / h, and 141.9 μmol / h, respectively. The above results show that the photocatalytic hydrogen production performance of g-C3N4 / UFR-NC composite nanomaterials is significantly better than that of pure g-C3N4, and that the photocatalytic hydrogen production rate of g-C3N4 / UFR-NC composite nanomaterials after loading of gold and palladium core-shell is somewhat greater than that of g-C3N4 / UFR-NC composite nanomaterials. From panel D of the figure, it can be seen that g-C3N4 / UFR-NC / Au@Pd composite nanomaterials do not change significantly after two cycles within 8 h, indicating that the photocatalytic hydrogen production performance of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials has good stability.

[0024] Experiment Four: Investigation of hydrogen release performance of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials. Figure 11Figure 1 shows the in vitro hydrogen release ability detection results of g-C3N4 / UFR-NC / Au@Pd after hydrogen was passed outside under the action of near-infrared laser irradiation or not. In the figure, A is the ultraviolet-visible absorption spectrum of different concentrations of methylene blue solution; B is the linear fitting standard curve of the absorption intensity of MB at 664 nm and the concentration of MB; C is the reaction process of g-C3N4 / UFR-NC / Au@Pd+H2 composite nanomaterials with MB without 808 nm near-infrared light irradiation; D is the reaction process of g-C3N4 / UFR-NC / Au@Pd+H2 composite nanomaterials with MB after 808 nm near-infrared light irradiation; E is the absorbance difference change of MB in the reaction solution of g-C3N4 / UFR-NC / Au@Pd+H2 composite nanomaterials under the action of 808 nm near-infrared light irradiation or not; F is the absorbance difference change of MB in the reaction solution of g-C3N4 / UFR-NC / Au@Pd after hydrogen was passed outside under the action of 808 nm near-infrared light irradiation or not (n=3). ****p<0.0001. As can be seen from A, MB has a characteristic absorption peak at 664 nm, and the absorbance value at 664 nm also increases with the increase of the concentration of MB solution. B also shows that the absorbance of MB solution changes with the concentration, and they have a linear correlation. According to C, D and E, it can be seen that under the action of 808 nm near-infrared light for the first 1 h, the absorbance value of MB at 664 nm in the g-C3N4 / UFR-NC / Au@Pd+H2 composite nanomaterial aqueous solution is faster than that of MB at 664 nm in the g-C3N4 / UFR-NC / Au@Pd+H2 composite nanomaterial aqueous solution without 808 nm near-infrared light irradiation, and the H2 release speed is faster than that of g-C3N4 / UFR-NC / Au@Pd+H2 composite nanomaterial aqueous solution without 808 nm near-infrared light irradiation. Subsequently, the H2 release speed of g-C3N4 / UFR-NC / Au@Pd+H2 composite nanomaterial aqueous solution under the action of 808 nm near-infrared light gradually slows down, while the hydrogen release speed of g-C3N4 / UFR-NC / Au@Pd+H2 composite nanomaterial aqueous solution without 808 nm near-infrared light irradiation gradually increases after 1 h, which shows that the effect of g-C3N4 / UFR-NC / Au@Pd+H2 composite nanomaterials releasing H2 without the action of 808 nm near-infrared light is obviously slower than that of g-C3N4 / UFR-NC / Au@Pd+H2 composite nanomaterial aqueous solution under the action of 808 nm near-infrared light.The absorbance difference change of MB in the reaction solution at 60 min after the g-C3N4 / UFR-NC / Au@Pd outside hydrogen gas in the presence or absence of 808 nm near-infrared light irradiation in F of the figure shows that the hydrogen release performance of the g-C3N4 / UFR-NC / Au@Pd+H2 composite nanomaterial can be obviously enhanced under the action of 808 nm near-infrared light irradiation (p<0.0001). The above results show that the reducing property of g-C3N4 / UFR-NC / Au@Pd+H2 is obviously enhanced under the action of 808 nm near-infrared light irradiation, which will be beneficial to the faster release of H2 of the nanomaterial at the lesion site in the in vivo experiment and may achieve better hydrogen treatment effect.

[0025] Experiment five: investigation of the in vitro photothermal performance of the g-C3N4 / UFR-NC / Au@Pd+H2 composite nanomaterial.

[0026] 1, extinction coefficient detection of g-C3N4 / UFR-NC / Au@Pd+H2 composite nanomaterial: Figure 12 The extinction coefficient detection results of g-C3N4 / UFR-NC, g-C3N4 / UFR-NC / Au@Pd and g-C3N4 / UFR-NC / Au@Pd+H2 composite nanomaterial. A, C and E in the figure are respectively the UV-Vis-NIR spectrum of g-C3N4 / UFR-NC, g-C3N4 / UFR-NC / Au@Pd and g-C3N4 / UFR-NC / Au@Pd+H2 composite nanomaterial at different concentrations; B, D and F in the figure are respectively the linear fitting curves of the absorbance at 808 nm and the concentration of g-C3N4 / UFR-NC composite nanomaterial, g-C3N4 / UFR-NC / Au@Pd and g-C3N4 / UFR-NC / Au@Pd+H2. It can be seen from A, C and E in the figure that g-C3N4 / UFR-NC, g-C3N4 / UFR-NC / Au@Pd composite nanomaterial and g-C3N4 / UFR-NC / Au@Pd+H2 all have strong absorption in the NIR-I region, and have obvious concentration dependence. At the same time, through comparison, the results show that g-C3N4 / UFR-NC / Au@Pd+H2 has stronger absorption at 808 nm than g-C3N4 / UFR-NC and g-C3N4 / UFR-NC / Au@Pd composite nanomaterial. Then, we linearly fit the nanomaterial concentration and the corresponding absorbance value at 808 nm (as shown in B, D and F in the figure), and calculate the extinction coefficient of different materials through the Lambert-Beer law. Finally, we obtain the corresponding extinction coefficients of g-C3N4 / UFR-NC, g-C3N4 / UFR-NC / Au@Pd and g-C3N4 / UFR-NC / Au@Pd+H2 composite nanomaterials as 4.81, 6.96 and 7.69 L·g-1 ·cm -1 It can be seen that the extinction coefficient of g-C3N4 / UFR-NC / Au@Pd+ H2 composite nanomaterial is the largest. For light absorption capacity, g-C3N4 / UFR-NC / Au@Pd+ H2 composite nanomaterial is stronger than g-C3N4 / UFR-NC and g-C3N4 / UFR-NC / Au@Pd composite nanomaterial.

[0027] 2. Temperature rising curve detection of g-C3N4 / UFR-NC / Au@Pd+ H2 composite nanomaterial: Figure 13 The results of in vitro photothermal performance detection of g-C3N4 / UFR-NC, g-C3N4 / UFR-NC / Au@Pd and g-C3N4 / UFR-NC / Au@Pd+ H2 composite nanomaterials. In the figure, A is the temperature rising curve diagram of g-C3N4 / UFR-NC / Au@Pd+ H2 with different concentrations (5, 15, 45 and 90 μg / mL) under the irradiation of 808 nm near-infrared laser with a power density of 0.5 W / cm 2 ; B is the temperature rising curve diagram of g-C3N4 / UFR-NC / Au@Pd+ H2 with the same concentration under the irradiation of 808 nm near-infrared laser with a power density of 0.5 W / cm 2 , 0.75 W / cm 2 and 1 W / cm 2 , respectively; C is the temperature rising curve diagram of g-C3N4 / UFR-NC, g-C3N4 / UFR-NC / Au@Pd and g-C3N4 / UFR-NC / Au@Pd+ H2 under the irradiation of 808 nm near-infrared laser with a power of 0.5 W / cm 2 ; D is the temperature rising difference column chart (n=3) of g-C3N4 / UFR-NC, g-C3N4 / UFR-NC / Au@Pd and g-C3N4 / UFR-NC / Au@Pd+ H2 under the irradiation of 808 nm near-infrared laser with a power of 0.5 W / cm 2 ****p<0.0001.

[0028] As can be seen from A in the figure, under the irradiation of the same near-infrared light power (0.5 W / cm 2 ), the photothermal conversion performance of g-C3N4 / UFR-NC / Au@Pd+ H2 nanomaterial aqueous solution with different concentrations increases with the increase of concentration. As can be seen from B in the figure, using different power densities (0.5, 0.75 and 1 W / cm 2The 808 nm laser of the NIR (near-infrared) irradiation system (NIR-808) was used to irradiate the nanomaterial aqueous solution of g-C3N4 / UFR-NC / Au@Pd+H2 for 10 min, and it was found by real-time detection of near-infrared light that the photo-thermal conversion performance of the g-C3N4 / UFR-NC / Au@Pd+H2 composite nanomaterial was better as the laser irradiation power density increased. As can be seen from the C in the figure, as the laser irradiation time was prolonged, the temperature of the nanomaterial aqueous solution of each group also gradually increased, and the photo-thermal performance of the g-C3N4 / UFR-NC / Au@Pd+H2 composite nanomaterial was significantly improved. Then, according to the D infrared thermal imager in the figure, the temperature difference column chart of the nanomaterials of different groups within 10 min was monitored, and it can be seen that the temperature of the g-C3N4 / UFR-NC solution increased by 7.3°C, the temperature of the g-C3N4 / UFR-NC / Au@Pd solution increased by 11.5°C, and the temperature of the g-C3N4 / UFR-NC / Au@Pd+H2 solution increased by 13.5°C, which further indicated that the photo-thermal conversion performance of the g-C3N4 / UFR-NC / Au@Pd+H2 group was significantly higher than that of the g-C3N4 / UFR-NC and g-C3N4 / UFR-NC / Au@Pd two groups.

[0029] Example 2: Use of the compound of Example 1 in the preparation of a medicament.

[0030] Experiment six: MTT method to explore the synergistic protective effect of g-C3N4 / UFR-NC / Au@Pd composite nanomaterial on damaged neurons. (1) After the primary neurons were cultured for 7 days, 6-OHDA with concentrations of 0.05, 0.1, 0.2, 0.4, and 0.8 mM was added to the primary neurons, which were then incubated in a 37°C incubator for 24 h to explore the appropriate concentration of 6-OHDA for inducing the in vitro PD model. The cell damage degree of the primary neurons was detected by the MTT method to explore the appropriate modeling concentration of 6-OHDA on the primary neurons. (2) According to the foregoing method, g-C3N4 / UFR-NC / Au@Pd composite nanomaterial aqueous solution with concentrations of 2.5, 5, 15, 45, and 90 μg / mL and 0.1 mM 6-OHDA solution were added to the cultured primary neurons, and the absorbance value of each group was detected by the MTT method to reflect the protective effect of g-C3N4 / UFR-NC / Au@Pd composite nanomaterial on damaged neurons. (3) Different materials (g-C3N4 / UFR-NC / Au@Pd, g-C3N4 / UFR-NC / Au@Pd+NIR, g-C3N4 / UFR-NC / Au@Pd+H2, g-C3N4 / UFR-NC / Au@Pd+H2+NIR) were explored, and the neurons were treated according to the foregoing method.

[0031] Figure 14MTT method exploration results; A in the figure is the MTT method to detect the effect of different concentrations of 6-OHDA on the cell viability of primary neurons. As shown in the figure, the primary neurons after modeling by 0.1 mM 6-OHDA can reach nearly 50% of the viability, which can be used for subsequent experiments of PD in vitro model. B in the figure is to detect the effect of different concentrations of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials on the cell viability of damaged neurons. As shown in the figure, after the primary neurons were treated with g-C3N4 / UFR-NC / Au@Pd composite nanomaterials with concentrations of 2.5, 5, 15, 45 and 90 μg / mL, respectively, the cell viability was improved compared with the 6-OHDA group, indicating that g-C3N4 / UFR-NC / Au@Pd composite nanomaterials had obvious protective effect on damaged neurons. In addition, the cell viability of the group treated with 15 μg / mL of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials was significantly improved (p<0.05) compared with the 6-OHDA group. Therefore, we finally selected 15 μg / mL as the final drug treatment concentration. C in the figure is the effect of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials combined with hydrogen-photo-thermal on the cell viability of damaged neurons. As can be seen from the figure: the MTT detection results show that the cell viability of the four material treatment groups is significantly improved compared with the 6-OHDA group, and the cell viability of the g-C3N4 / UFR-NC / Au@Pd+H2+NIR group is more significantly improved than that of the other three material treatment groups, indicating that g-C3N4 / UFR-NC / Au@Pd composite nanomaterials combined with hydrogen-photo-thermal have strong synergistic protective effect on damaged neurons.

[0032] Experiment seven: Calcein-AM / PI method to explore the effect of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials on cell viability. (1) 0.1 mM 6-OHDA solution and different concentrations of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials were used to treat primary neurons for 24 h, and then Calcein-AM / PI live and dead cell staining was performed. (2) 6-OHDA and different groups of materials were used to treat cells, and the concentration of 6-OHDA was 0.1 mM, and the concentration of material treatment was 15 μg / mL.

[0033] Figure 15Calcein-AM / PI staining results of the effect of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials on damaged neurons. As can be seen from Figure A, the green fluorescence of the Control group is the strongest, and the number of living cells is the most. The number of living cells of the 6-OHDA group is significantly reduced compared with the Control group, and the red fluorescence is the strongest, and the number of dead cells is the most. The number of living cells of the different material treatment groups is significantly increased, and the number of dead cells is significantly reduced compared with the 6-OHDA group. In addition, as can be seen from the statistical results in Figures B and C, the green fluorescence-labeled living cells gradually increase, and the red fluorescence-labeled dead cells decrease with the increase of the concentration of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials, and there are statistical differences, indicating that g-C3N4 / UFR-NC / Au@Pd composite nanomaterials itself has a significant protective effect on damaged neurons.

[0034] Figure 16 Calcein-AM / PI staining results of the effect of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials combined with hydrogen-galvanic effect on damaged neurons. As can be seen from Figure A, the green fluorescence of the Control group is the strongest, and the number of living cells is the most. The number of living cells of the 6-OHDA group is significantly reduced compared with the Control group, and the red fluorescence is the strongest, and the number of dead cells is the most. As can be seen from the statistical results in Figures B and C, the number of living cells of the different material treatment groups is significantly increased, and the number of dead cells is significantly reduced compared with the 6-OHDA group. The green fluorescence-labeled living cells of the g-C3N4 / / UFR-NC / Au@Pd+H2+NIR group are the most, and the red fluorescence-labeled dead cells are the least compared with other treatment groups. It is indicated that g-C3N4 / / UFR-NC / Au@Pd composite nanomaterials combined with hydrogen-galvanic effect have a significant synergistic protective effect on damaged neurons.

[0035] Experiment eight: ROS staining method to explore the effect of g-C3N4 / / UFR-NC / Au@Pd composite nanomaterials on the intracellular ROS level. (1) 0.1 mM 6-OHDA solution and different concentrations of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials were used to treat primary neurons for 24 h, and then ROS fluorescent probe was performed. (2) ROS cell staining was performed on each treatment group of cells, and the concentration of 6-OHDA was 0.1 mM, and the concentration of material treatment was 15 μg / mL. Figure 17ROS staining results of the effect of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials on damaged neurons. As can be seen from Figure A, after observing under a fluorescence microscope, the green fluorescence of the primary neurons induced by 6-OHDA was enhanced, indicating that the ROS activity level in the cells was increased. Compared with the 6-OHDA group, the green fluorescence of the different concentrations of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials treatment groups was weakened to different degrees, indicating that the ROS activity level in the cells was reduced. With the increase of the concentration of the nanomaterials, the ROS activity level was reduced, and the statistical results can be seen from Figure B. It is shown that there is a statistical difference. It is shown that g-C3N4 / UFR-NC / Au@Pd composite nanomaterials can reduce the oxidative stress level of cells and have a significant protective effect on damaged neurons. Figure C is the ROS staining results of the effect of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials combined with hydrogen-light heat on damaged neurons. It can be seen that compared with the 6-OHDA group, the ROS activity level in the cells of the four material treatment groups is reduced, and the ROS activity level in the cells of the g-C3N4 / UFR-NC / Au@Pd+H2+NIR group is the lowest. The statistical results are shown in Figure D. It is further shown that g-C3N4 / UFR-NC / Au@Pd composite nanomaterials combined with hydrogen-light heat can reduce the oxidative stress level of cells and have a more obvious protective effect on damaged neurons than the other three material treatment groups.

[0036] Experiment Nine: qPCR and ELISA methods were used to detect the inflammatory inhibition effect of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials combined with hydrogen-light heat on activated BV2 cells 9.1. qPCR method was used to detect the polarization of BV2 microglial cells: qPCR method was used to detect the mRNA level of M1 / M2 type markers iNOS / Arg1 of BV2 cells (induced by 6-OHDA) treated by each group of materials. qPCR analysis was performed using Power SYBR Green PCR Master Mix. Figure 18Figure 6 shows the results of detecting the iNOS / Argl mRNA expression levels of BV2 cells after 6-OHDA induction and g-C3N4 / UFR-NC / Au@Pd composite nanomaterials combined with hydrogen-photothermal treatment. A in the figure is iNOS, and B in the figure is Argl. As can be seen from the figure, after 6-OHDA-induced microglial cells were treated with each group of materials, the mRNA expression level of the M2-type microglial cell marker Argl increased, while the mRNA expression level of the Ml-type microglial cell marker iNOS decreased. The results of the g-C3N4 / UFR-NC / Au@Pd composite nanomaterials combined with hydrogen-photothermal group were the most significant relative to other material groups, indicating that the g-C3N4 / UFR-NC / Au@Pd composite nanomaterials combined with hydrogen-photothermal significantly reshaped the microglial cell phenotype from Ml to M2 9.2, Enzyme-linked immunosorbent assay (ELISA) method for determining the level of BV2 microglial cell inflammatory factors: the concentration of pro-inflammatory factors IL-1β, IL-6, TNF-α in the culture supernatant of BV2 cells (6-OHDA induction) treated with each group of materials was determined by ELISA method. After 6-OHDA induction for 24 h, BV2 cells cultured in a 6-well plate were added with each group of materials for a total of 24 h of incubation, and then detected. The protein concentration was determined by BCA protein determination method. The concentration of pro-inflammatory factors IL-1β, IL-6, TNF-α was determined using an ELISA kit. Figure 19 Figure 6 shows the results of detecting the iNOS / Argl mRNA expression levels of BV2 cells after 6-OHDA induction and g-C3N4 / UFR-NC / Au@Pd composite nanomaterials combined with hydrogen-photothermal treatment. A in the figure is iNOS, and B in the figure is Argl. As can be seen from the figure, after 6-OHDA-induced microglial cells were treated with each group of materials, the mRNA expression level of the M2-type microglial cell marker Argl increased, while the mRNA expression level of the Ml-type microglial cell marker iNOS decreased. The results of the g-C3N4 / UFR-NC / Au@Pd composite nanomaterials combined with hydrogen-photothermal group were the most significant relative to other material groups, indicating that the g-C3N4 / UFR-NC / Au@Pd composite nanomaterials combined with hydrogen-photothermal significantly reshaped the microglial cell phenotype from Ml to M2

[0037] Experiment ten: in vivo fluorescence imaging to explore the appropriate light time after intranasal administration of nanomaterials in mice. The in vivo fluorescence imaging instrument was used to explore the fluorescence intensity of nanomaterials in the brain of mice after intranasal administration. Figure 20 The in vivo fluorescence imaging detection results of mice intranasally administered with RhB@ g-C3N4 / UFR-NC / Au@Pd composite nanomaterials at different times. As can be seen from A in the figure, a part of the nanomaterials has reached the brain of the mice 1 h after administration. With the increase of time, the fluorescence intensity of the brain of the mice is stronger and stronger, reflecting that the accumulation of nanomaterials in the brain is more and more, and the fluorescence intensity in the brain is stronger when tested 6 h after administration. Subsequently, when tested 24 h after administration, the fluorescence intensity in the brain of the mice is obviously weaker than that 6 h after administration. After that, with the extension of time, the fluorescence intensity in the brain gradually decreases. This also shows that the nanomaterials will not accumulate in the brain for a long time, and the biological safety is high. B in the figure is the statistical analysis results of the fluorescence intensity of the brain of the mice at different time points before and after administration.

[0038] Experiment eleven: animal behavior experiment to explore the therapeutic effect of g-C3N4 / UFR-NC / Au@Pd composite nanomaterials combined with hydrogen-gas photothermal on PD mice. The open field experiment, pole climbing experiment and apomorphine (APO) rotation experiment were carried out on the PD mice, respectively. Figure 21The results of the animal behavior experiment of the g-C3N4 / UFR-NC / Au@Pd composite nanomaterial combined with hydrogen-light-heat on PD mice are shown in the figure. A in the figure is the route map of the mice in the open field for 5 min, indicating the autonomous activity ability of the mice. It can be seen from the figure that the autonomous activity amount of the PD group mice is significantly reduced compared with the Control group mice, and tends to move around the periphery of the open field or be stationary, while the activity amount of the material treated group mice is significantly increased, the activity is more active, and the activity in the central area is also significantly increased. B-D in the figure are respectively the statistical graphs of the total distance traveled by the mice, the average speed and the total area resting time (n=3). The statistical graph results show that the total travel distance of the PD group mice is significantly reduced, the average speed is significantly reduced, and the total area resting time is significantly increased compared with the Control group, indicating that the PD model is successfully established. Compared with the PD group mice, the total travel distance of the material treated group is significantly increased, the average speed is significantly increased, and the total area resting time is significantly reduced, and the overall statistics of the g-C3N4 / UFR-NC / Au@Pd+H2+NIR group are more significant than those of the g-C3N4 / UFR-NC / Au@Pd group and the g-C3N4 / UFR-NC / Au@Pd+NIR group. From the above results, it can be seen that the g-C3N4 / UFR-NC / Au@Pd composite nanomaterial combined with hydrogen-light-heat can significantly change the autonomous activity ability of the PD mice, reduce the anxiety of the PD mice to the new environment, and has a significant therapeutic effect on the PD mice. E in the figure is the pole climbing experiment result graph of the g-C3N4 / UFR-NC / Au@Pd composite nanomaterial combined with hydrogen-light-heat on PD mice. F in the figure is the APO rotation experiment result graph of the g-C3N4 / UFR-NC / Au@Pd composite nanomaterial combined with hydrogen-light-heat on PD mice. As shown in E and F in the figure, the pole climbing time of the PD group mice is significantly prolonged, and the APO rotation number is significantly increased compared with the Control group mice, indicating that the PD mice have been successfully modeled. Compared with the PD group mice, the pole climbing time of the material treated group mice is reduced to different degrees, and the APO rotation number is also significantly reduced, all with statistical differences, and the g-C3N4 / UFR-NC / Au@Pd+H2+NIR group has the best effect.

[0039] Experiment twelve: Western blotting experiment to explore the protective effect of the g-C3N4 / UFR-NC / Au@Pd composite nanomaterial combined with hydrogen-light-heat on the neurons of PD mice. The MAP2 and Caspase 3 protein expression levels in the brain tissues of mice in different experimental groups were detected by Western blotting. Figure 22Figure 1 is a result diagram of Western blotting experiment of the effect of g-C3N4 / UFR-NC / Au@Pd composite nanomaterial combined with hydrogen-photothermal on PD mice. A of the figure is the MAP2 and Caspase 3 protein band result diagram of the brain tissue of mice in each treatment group; B and C of the figure are respectively the MAP2 / β-actin and Caspase 3 / β-actin protein expression level statistical diagram (n=3). *p<0.05, **p<0.01. As shown in A and B of the figure, compared with the normal control group, the MAP2 expression level of the PD group decreased obviously, and compared with the PD group, the MAP2 protein expression level of the four material treatment groups increased in different degrees. Among them, the MAP2 expression level of the PD+ g-C3N4 / UFR-NC / Au@Pd+ H2+NIR group decreased most obviously compared with the PD group (P<0.01). As can be seen from A and C of the figure, compared with the normal control group, the Caspase 3 expression level of the PD group increased obviously, and compared with the PD group, the Caspase 3 protein expression level of the four material treatment groups decreased in different degrees. Among them, the Caspase 3 expression level of the PD+ g-C3N4 / UFR-NC / Au@Pd+ H2+NIR group decreased most obviously compared with the PD group (P<0.01). Therefore, it can be known that g-C3N4 / UFR-NC / Au@Pd composite nanomaterial combined with hydrogen-photothermal can inhibit neuron apoptosis and reduce the damage of 6-OHDA to neurons, and has obvious treatment effect on PD mice.

Claims

1. A gold-palladium-nitrogen-doped carbon tape-modified g-C3N4 nanosheet, characterized in that, UFR-NC is doped in g-C3N4 to form g-C3N4 / UFR-NC composite nanomaterial; gold-palladium shell-core particles are loaded on the g-C3N4 / UFR-NC composite nanomaterial by taking the g-C3N4 / UFR-NC composite nanomaterial as a carrier. 2.The gold-palladium-nitrogen-doped carbon wire belt modified g-C3N4 nanosheet according to claim 1, wherein, The gold-palladium shell-core particles have gold as a core and palladium as a shell.

3. The gold-palladium-nitrogen-doped carbon filament tape-modified g-C3N4 nanosheet according to claim 1, characterized in that, The diameter of the gold-palladium shell-core particles is 20-30 nm.

4. A method for preparing the gold-palladium-nitrogen-doped carbon filament tape modified g-C3N4 nanosheet according to any one of claims 1 to 3, characterized in that, The preparation method comprises the following steps: S1, preparing nitrogen-doped carbon ribbon modified graphite phase carbon nitride; S2, the nitrogen-doped carbon filament modified graphite phase carbon nitride is dissolved in water, sodium citrate solution, gold chloride trihydrate and Na2PdC l4 The solution is stirred and mixed, ascorbic acid is added for reaction, and drying to obtain gold-palladium-nitrogen-doped carbon filament modified g-C3N4 nanosheet.

5. The preparation method according to claim 4, characterized in that, The S1 comprises the following steps: S1-1, urea is placed in a crucible and heated, and is kept in an oil bath to obtain a transparent melted urea solution; S1-2, UFR is added into the urea solution to form a uniform solution, and a solid powder is obtained by condensation; S1-3, the solid powder is calcined in a tube furnace at a temperature increasing rate of 5 ℃ / min for 3 h at 600 ℃ to obtain nitrogen-doped carbon ribbon modified graphite phase carbon nitride.

6. The preparation method according to claim 4, characterized in that, The S2 comprises the following steps: S2-1, PdCl2and NaCl were dissolved, heated to 90°C and stirred for 30 min to obtain Na2PdCl6 l4 solution; S2-2, the graphite phase carbon nitride modified by nitrogen-doped carbon filament strips is dissolved in water, and a sodium citrate solution, gold chloride trihydrate and Na2PdC l4 The reaction system is obtained by stirring and mixing the solution. S2-3, ascorbic acid is dissolved in water, and is added into the reaction system at a speed of 2 mL / h by using a syringe pump to perform a reaction; after the reaction liquid is centrifuged to remove supernatant and is dried, gold@palladium-nitrogen-doped carbon ribbon modified g-C3N4 nanosheets are obtained.

7. Use of the gold@palladium-nitrogen-doped carbon ribbon modified g-C3N4 nanosheets in any one of claims 1 to 3 in the preparation of a drug for protecting neurons.

8. Use of the gold@palladium-nitrogen-doped carbon ribbon modified g-C3N4 nanosheets in any one of claims 1 to 3 in the preparation of a drug for inhibiting neuroinflammation.

9. Use according to claim 8, characterized in that, The neuroinflammation is neuroinflammation caused by Parkinson's disease, Alzheimer's disease, brain trauma and / or stroke.

10. Use of the gold@palladium-nitrogen-doped carbon ribbon modified g-C3N4 nanosheets in any one of claims 1 to 3 in the preparation of a drug for reducing oxidative stress damage in vivo.

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