Method for improving stability of metal gallium nanoparticles and metal gallium nanoparticles

Abstract

The invention discloses a method for improving the stability of metal gallium nanoparticles, which comprises the following preparation steps: S1, preparing black phosphorus nanosheets: adding black phosphorus into N-methyl pyrrolidone, carrying out ultrasonic treatment in an ice bath to obtain a dispersion liquid, centrifuging, collecting precipitates, washing the precipitates, and freeze-drying to obtain the black phosphorus nanosheets; s2, preparing modified metal gallium nanoparticles: adding liquid metal gallium elementary substances into ethylene glycol, adding diluted hydrochloric acid, performing ultrasonic treatment, adding the black phosphorus nanosheets, performing ultrasonic treatment in an ice bath, centrifuging, collecting precipitates, washing the precipitates, and performing freeze drying to obtain the black phosphorus nanosheet modified metal gallium nanoparticles. The black phosphorus nanosheet modified metal gallium nanoparticles prepared by the preparation method disclosed by the invention show excellent long-term stability and total oxidation resistance, and in addition, the black phosphorus nanosheet modified metal gallium nanoparticles also show long-term stable photo-thermal performance under near-infrared irradiation, so that the application of the black phosphorus nanosheet modified metal gallium nanoparticles in the field of biomedicine is greatly expanded.

Description

Technical Field

[0001] The present invention belongs to the technical field of biomedical materials, and more particularly, relates to a method for improving the stability of metal gallium nanoparticles and the metal gallium nanoparticles. Background Art

[0002] Gallium (Ga) has unique physical and chemical properties. It is liquid at room temperature and pressure, with a melting point of only 29.76°C. This characteristic distinguishes it from most metals. In the field of electronics, it can be used to manufacture liquid metal electronic devices, giving the devices deformability and self-repairing capabilities, and promoting the development of flexible electronics. In recent years, Ga has shown unique application potential in the field of biomedical photothermal therapy, especially metal gallium nanoparticles, which have received widespread attention. Metal gallium nanoparticles have good biocompatibility and low cytotoxicity. When the size of metal gallium nanoparticles is significantly smaller than the wavelength of the incident light, a surface plasmon resonance effect occurs, resulting in a sharp increase in the local electric field, which in turn triggers a photothermal effect. Under light irradiation, the local temperature rises rapidly to achieve precise killing of bacteria or tumor cells. The photothermal conversion efficiency of metal gallium nanoparticles is mainly affected by factors such as size, shape, and surface chemistry. In air, the surface of Ga slowly oxidizes to form a protective film of gallium oxide (Ga2O3), but in aqueous solution, especially corrosive media, the stability of Ga decreases, oxidation is accelerated, and products such as Ga2O3 and gallium oxyhydroxyl (GaOOH) are easily generated. These oxidation products will cause the surface properties, shape and size of Ga to change, which will have an adverse effect on the application of metal gallium nanoparticles in the field of biomedical photothermal therapy. Summary of the Invention

[0003] The purpose of the present invention is to provide a method for improving the stability of metal gallium nanoparticles and metal gallium nanoparticles.

[0004] In a first aspect, the present invention provides a method for improving the stability of metal gallium nanoparticles, comprising the following preparation steps:

[0005] S1. Preparation of black phosphorus nanosheets: black phosphorus was added to N-methylpyrrolidone and sonicated in an ice bath to obtain a dispersion. The precipitate was collected after centrifugation, washed, and freeze-dried to obtain black phosphorus nanosheets.

[0006] S2. Preparation of modified metal gallium nanoparticles: adding liquid metal gallium to ethylene glycol, adding dilute hydrochloric acid, and then adding the black phosphorus nanosheets after ultrasonic treatment. After ultrasonic treatment in an ice bath, the precipitate is collected by centrifugation, washed, and freeze-dried to obtain metal gallium nanoparticles modified with black phosphorus nanosheets.

[0007] Optionally, step S1 includes:

[0008] S1-1. Grinding black phosphorus crystals into black phosphorus flakes;

[0009] S1-2. The black phosphorus flakes were added to N-methylpyrrolidone and ultrasonically treated in an ice bath to form a dispersion;

[0010] S1-3. The dispersion was centrifuged, and the precipitate was collected, washed, and freeze-dried to prepare black phosphorus nanosheets.

[0011] Optionally, in step S1-1, the black phosphorus crystals are ground into black phosphorus flakes with a particle size of less than 3 mm.

[0012] Optionally, in step S1-2, the mass volume ratio of black phosphorus flakes and N-methylpyrrolidone is 10-30 mg:10-60 ml.

[0013] Optionally, in step S1-2, the ultrasonic treatment power is 50 to 150 W, and the ultrasonic treatment time is 5 to 20 h; and / or;

[0014] In step S2, the power of the ultrasonic treatment is 50 to 150 W, the time of the ultrasonic treatment is 0.5 to 6 h after the addition of dilute hydrochloric acid, and the time of the ultrasonic treatment is 0.5 to 6 h after the addition of black phosphorus nanosheets.

[0015] Optionally, the black phosphorus nanosheets have a particle size of 0.1 to 15 μm and a thickness of less than 100 nanometers.

[0016] Optionally, in step S2, the mass-to-volume ratio of the liquid metal gallium, ethylene glycol, dilute hydrochloric acid and black phosphorus nanosheets is 30-50 mg: 20-80 ml: 10-40 ul: 5-15 mg.

[0017] Optionally, in step S2, the mass-to-volume ratio of the liquid metal gallium, ethylene glycol, dilute hydrochloric acid and black phosphorus nanosheets is 35-45 mg: 30-50 ml: 15-25 ul: 8-12 mg.

[0018] Optionally, in step S2, the particle size of the metal gallium nanoparticles is 100 to 400 nm.

[0019] In a second aspect, the present invention provides a metal gallium nanoparticle with high stability, which is prepared by the aforementioned method for improving the stability of metal gallium nanoparticles.

[0020] In summary, the present invention has at least one of the following beneficial effects:

[0021] 1. The present invention provides a method for improving the stability of metal gallium nanoparticles. The metal gallium nanoparticles are modified by black phosphorus nanosheets to improve the total antioxidant capacity and stability of the gallium nanoparticles. In subsequent examples, the metal gallium nanoparticles modified with black phosphorus nanosheets can maintain the same physical phase and micromorphology as before immersion after being immersed in deionized water for 10 days, and can maintain excellent photothermal properties under near-infrared (NIR) irradiation. In addition, the modified metal gallium nanoparticles still maintain excellent total antioxidant properties after being immersed in deionized water for 30 days.

[0022] 2. The present invention provides a highly stable metal gallium nanoparticle. By optimizing the modification process of the metal gallium nanoparticles, the long-term antioxidant performance and stability of the metal gallium nanoparticles can be further improved. The metal gallium nanoparticles with excellent long-term antioxidant performance, stability and photothermal performance have broad application prospects in biomedical fields such as bacterial infection, tumor, osteoporosis, diabetic bone defect and diabetic wound treatment. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 These are photos of black phosphorus nanosheets modified with different BP and Ga mass ratios prepared in Examples 1 to 5 of the present invention, and of metal gallium nanoparticles immersed in deionized water for 0, 2, and 4 hours;

[0024] Figure 2 Transmission electron microscopy (TEM) images of BP nanosheets and black phosphorus nanosheets modified metal gallium nanoparticles (BP@Ga) prepared in Comparative Example 1 and Example 4 of the present invention, respectively;

[0025] Figure 3 Optical photographs of BP nanosheets, Ga nanoparticles, and black phosphorus nanosheet-modified metal gallium nanoparticles (BP@Ga) prepared in Comparative Examples 1 and 2 and Example 4 of the present invention, respectively, immersed in deionized water for different times;

[0026] Figure 4 Scanning electron microscope (SEM) images of Ga nanoparticles prepared in Comparative Example 2 of the present invention after being immersed in deionized water for different times;

[0027] Figure 5 Scanning electron microscope (SEM) images of black phosphorus nanosheet-modified gallium nanoparticles (BP@Ga) prepared in Example 4 of the present invention after being immersed in deionized water for different times;

[0028] Figure 6 X-ray diffraction patterns (XRD; a) and Fourier transform infrared spectra (FTIR; b) of BP nanosheets, Ga nanoparticles, and black phosphorus nanosheet-modified gallium nanoparticles (BP@Ga) prepared in Comparative Examples 1 and 2 and Example 4 of the present invention after being immersed in deionized water for 10 days;

[0029] Figure 7 Qualitative photos of the total antioxidant performance of BP nanosheets, Ga nanoparticles, and black phosphorus nanosheet-modified gallium nanoparticles (BP@Ga) prepared in Comparative Examples 1 and 2 and Example 4 of the present invention, respectively, after being immersed in deionized water for different times;

[0030] Figure 8 The photothermal properties of BP nanosheets, Ga nanoparticles and black phosphorus nanosheet-modified metal gallium nanoparticles (BP@Ga) prepared in Comparative Examples 1 and 2 and Example 4 of the present invention, respectively, after being immersed in deionized water for 0 days and 10 days. DETAILED DESCRIPTION

[0031] The present invention provides a method for improving the stability of metal gallium nanoparticles and metal gallium nanoparticles. To clarify the objectives, technical solutions, and effects of the present invention, the present invention is described in further detail below. It should be understood that the specific embodiments described herein are intended only to illustrate the present invention and are not intended to limit the present invention.

[0032] Existing research reports have shown that metal Ga nanoparticles have a typical photothermal effect, which can convert the absorbed near-infrared light energy into local thermal energy, and be applied to the field of biomedical photothermal therapy, effectively using local thermal energy to kill bacteria or tumor cells. However, metal Ga nanoparticles are easily affected by environmental factors and change their surface properties, such as oxidation, agglomeration, etc., which will adversely affect the long-term stability and photothermal performance of metal Ga nanoparticles. During the long-term experimental research process, the applicant has originality proposed a method for modifying metal Ga nanoparticles using black phosphorus (BP) nanosheets, thereby improving the long-term stability and photothermal performance of metal Ga nanoparticles. The present invention is obtained on the basis of this research.

[0033] In some embodiments of the present invention, a method for improving the stability of metal gallium nanoparticles is provided, characterized by comprising the following preparation steps:

[0034] S1. Preparation of black phosphorus nanosheets: black phosphorus was added to N-methylpyrrolidone and sonicated in an ice bath to obtain a dispersion. The precipitate was collected after centrifugation, washed, and freeze-dried to obtain black phosphorus nanosheets.

[0035] S2. Preparation of modified metal gallium nanoparticles: adding liquid metal gallium to ethylene glycol, adding dilute hydrochloric acid, and then adding the black phosphorus nanosheets after ultrasonic treatment. After ultrasonic treatment in an ice bath, the precipitate is collected by centrifugation, washed, and freeze-dried to obtain metal gallium nanoparticles modified with black phosphorus nanosheets.

[0036] In some embodiments of the present invention, step S1. includes:

[0037] S1-1. Grinding black phosphorus crystals into black phosphorus flakes;

[0038] S1-2. The black phosphorus flakes were added to N-methylpyrrolidone and ultrasonically dispersed under an ice bath to form a dispersion;

[0039] S1-3. The dispersion was centrifuged, and the precipitate was collected, washed, and freeze-dried to prepare black phosphorus nanosheets.

[0040] In some embodiments of the present invention, in step S1-1, the black phosphorus crystals are ground into black phosphorus flakes with a particle size of less than 3 mm.

[0041] In some embodiments of the present invention, in step S1-2, the mass volume ratio of black phosphorus flakes and N-methylpyrrolidone is 10-30 mg:10-60 ml, preferably 15-25 mg:15-35 ml.

[0042] In some embodiments of the present invention, in step S1-2, the power of the ultrasonic treatment is 50-150W, and the ultrasonic treatment time is 5-20h; preferably, the power of the ultrasonic treatment is 60-90W, and the ultrasonic treatment time is 8-13h; preferably, the ultrasonic treatment lasts for 13-18s with a break of 1-3s. In step S2, the power of the ultrasonic treatment is 50-150W, and after adding dilute hydrochloric acid, the ultrasonic treatment time is 0.5-6h, preferably 0.5-3h; after adding black phosphorus nanosheets, the ultrasonic treatment time is 0.5-6h, preferably 0.5-3h; preferably, the ultrasonic treatment power is 60-90W; preferably, the ultrasonic treatment lasts for 13-18s with a break of 1-3s.

[0043] In some embodiments of the present invention, the black phosphorus nanosheets have a particle size of 0.1 to 15 μm and a thickness of less than 100 nanometers. Preferably, the black phosphorus nanosheets have a particle size of 1 to 5 μm and a thickness of less than 100 nm; more preferably, the black phosphorus nanosheets have a particle size of 1.5 to 3.5 μm and a thickness of less than 100 nm.

[0044] In some embodiments of the present invention, in step S2., the mass-to-volume ratio of the liquid metal gallium, ethylene glycol, dilute hydrochloric acid, and black phosphorus nanosheets is 30-50 mg: 20-80 ml: 10-40 ul: 5-15 mg.

[0045] In some embodiments of the present invention, in step S2., the mass-to-volume ratio of the liquid metal gallium, ethylene glycol, dilute hydrochloric acid, and black phosphorus nanosheets is 35-45 mg: 30-50 ml: 15-25 ul: 8-12 mg.

[0046] In some embodiments of the present invention, in step S2., the particle size of the metal gallium nanoparticles is 100-400 nm.

[0047] The present invention is further described in detail below with reference to specific examples and comparative examples. In the specific examples of the present invention, raw materials are commercially available unless otherwise specified.

[0048] Example 1

[0049] Example 1 provides a method for improving the stability of metal gallium nanoparticles and metal gallium nanoparticles, which specifically include the following steps:

[0050] S1. Preparation of black phosphorus nanosheets: adding black phosphorus to N-methylpyrrolidone, ultrasonically treating in an ice bath to obtain a dispersion, collecting a precipitate after centrifugation, washing the precipitate, and freeze-drying to prepare black phosphorus nanosheets; comprising:

[0051] S1-1. Black phosphorus crystals (BP, Pioneer Nano, 99.998% purity) were manually ground into black phosphorus flakes with a particle size of less than 3 mm using an agate mortar;

[0052] S1-2. Black phosphorus flakes were added to N-methylpyrrolidone (NMP, CAS No. 872-50-4) at a mass volume ratio of 20 mg:20 mL. The mixture was then sonicated in an ice bath (0°C to 4°C) to form a dispersion. The sonication time was 11 h at a power of 75 W, with a duration of 15 seconds and a rest period of 2 seconds.

[0053] S1-3. The above dispersion was centrifuged at 11000 rpm for 16 min, the precipitate was collected, washed twice with deionized water, and then placed in a -90°C vacuum freeze dryer for 10 h to prepare black phosphorus (BP) nanosheets.

[0054] S2. Preparation of modified metal gallium nanoparticles: Liquid metal gallium (Ga) elemental substance (Aladdin, purity 99.99%) was added to ethylene glycol (Aladdin, purity 98%), and after adding dilute hydrochloric acid, it was treated with ultrasound (power 75W, continuous 15s and interval 2s) for 2h, and then black phosphorus nanosheets were added. The mass volume ratio of liquid metal gallium (Ga) elemental substance, ethylene glycol, dilute hydrochloric acid and black phosphorus nanosheets was: 10mg:40ml:20ul (1M):10mg. After ultrasound (power 75W, continuous 15s and interval 2s) for 1h in an ice bath (0℃~4℃), the precipitate was collected after centrifugation at 11000rpm for 16min. The precipitate was washed twice with deionized water, freeze-dried, and then stored at -20℃ to prepare a black phosphorus (BP) nanosheet modified metal gallium (Ga) nanoparticle sample (BP@Ga). The sample was marked as 1:1 according to the mass ratio of BP and Ga.

[0055] Example 2

[0056] The difference between Example 2 and Example 1 is that, in S2. the preparation of modified metal gallium nanoparticles, the mass volume ratio of liquid metal gallium (Ga) element, ethylene glycol, dilute hydrochloric acid and black phosphorus nanosheets is: 20 mg: 40 ml: 20 ul (1 M): 10 mg, and the remaining preparation steps are the same as in Example 1, and a black phosphorus (BP) nanosheet modified metal gallium (Ga) nanoparticle (BP@Ga) sample is prepared, which is marked as sample 1:2 according to the mass ratio of BP and Ga.

[0057] Example 3

[0058] The difference between Example 3 and Example 1 is that, in S2. preparing modified metal gallium nanoparticles, the mass volume ratio of liquid metal gallium (Ga) element, ethylene glycol, dilute hydrochloric acid and black phosphorus nanosheets is: 30 mg: 40 ml: 20 ul (1M): 10 mg, and the remaining preparation steps are the same as in Example 1, and a black phosphorus (BP) nanosheet modified metal gallium (Ga) nanoparticle (BP@Ga) sample is prepared, which is marked as sample 1:3 according to the mass ratio of BP and Ga.

[0059] Example 4

[0060] The difference between Example 4 and Example 1 is that, in S2. preparing modified metal gallium nanoparticles, the mass volume ratio of liquid metal gallium (Ga) element, ethylene glycol, dilute hydrochloric acid and black phosphorus nanosheets is: 40 mg: 40 ml: 20 ul (1M): 10 mg, and the remaining preparation steps are the same as in Example 1, and a black phosphorus (BP) nanosheet modified metal gallium (Ga) nanoparticle (BP@Ga) sample is prepared, which is marked as sample 1:4 according to the mass ratio of BP and Ga.

[0061] Example 5

[0062] The difference between Example 5 and Example 1 is that, in S2. preparing modified metal gallium nanoparticles, the mass volume ratio of liquid metal gallium (Ga) element, ethylene glycol, dilute hydrochloric acid and black phosphorus nanosheets is: 50 mg: 40 ml: 20 ul (1M): 10 mg, and the remaining preparation steps are the same as in Example 1, and a black phosphorus (BP) nanosheet modified metal gallium (Ga) nanoparticle (BP@Ga) sample is prepared, which is marked as sample 1:5 according to the mass ratio of BP and Ga.

[0063] Comparative Example 1

[0064] Comparative Example 1 provides a method for preparing black phosphorus (BP) nanosheets, which specifically includes the following steps:

[0065] S1-1. Black phosphorus crystals (BP, Pioneer Nano, 99.998% purity) were manually ground into black phosphorus flakes with a particle size of less than 3 mm using an agate mortar;

[0066] S1-2. Black phosphorus flakes were added to N-methylpyrrolidone (NMP, CAS No.: 872-50-4) at a mass volume ratio of 20 mg:20 mL. The mixture was then ultrasonically treated in an ice bath (0°C to 4°C) to form a dispersion. The ultrasonic dispersion time was 11 h at a power of 75 W, with a duration of 15 s and a rest period of 2 s.

[0067] S1-3. The above dispersion was centrifuged at 11000 rpm for 16 min, the precipitate was collected, washed twice with deionized water, and then placed in a -90°C vacuum freeze dryer for 10 h to prepare black phosphorus (BP) nanosheets.

[0068] Comparative Example 2

[0069] Comparative Example 2 provides a method for preparing metal gallium nanoparticles, which specifically includes the following steps:

[0070] 40 mg of liquid metal gallium (Ga) element (Aladdin, purity 99.99%) was added to 40 ml of ethylene glycol (Aladdin, purity 98%), and 20 ul of 1 M dilute hydrochloric acid was added. The mixture was treated with ultrasound (power 75 W, continuous 15 s, rest 2 s) for 2 h, and then centrifuged at 11000 rpm for 16 min. The precipitate was collected, washed twice with deionized water, freeze-dried, and then stored at -20°C to obtain a Ga nanoparticle sample. The sample is used as Ga nanodroplets at room temperature.

[0071] 1 mg of the above samples of Examples 1 to 5 (1:1, 1:2, 1:3, 1:4 and 1:5) were respectively placed in different 1.5 ml EP tubes. 1 ml of deionized water was added to each EP tube. A probe sonicator was used with an ultrasonic power of 75 W and an ultrasonic time of 15 s to prepare 5 dispersions. The dispersions were allowed to stand for 0 h, 2 h, and 4 h, and photographed and recorded. The results are shown in the figure. Figure 1 shown.

[0072] from Figure 1 It can be seen that among the BP nanosheets modified Ga nanoparticles at different BP and Ga mass ratios, the sample with a BP and Ga mass ratio of 1:4 in Example 4 is less likely to settle in deionized water and has better stability.

[0073] The microstructures of the BP nanosheets of Comparative Example 1 and the BP-modified Ga (BP@Ga) nanoparticles of Example 4 were characterized by TEM. Figure 2As shown, it can be observed that the particle size of the BP nanosheets in Comparative Example 1 is 1.5-3.5 μm, and the thickness is less than 100 nm; in the BP@Ga sample of Example 4, the Ga nanoparticles are uniformly dispersed on the surface of the BP nanosheets, the particle size of the Ga nanoparticles is 100-400 nm, and the particle size of the BP nanosheets is 1.5-3.5 μm, and the thickness is less than 100 nm.

[0074] 1 mg of BP-modified Ga (BP@Ga) nanoparticles of Example 4, BP nanosheets of Comparative Example 1, and Ga nanoparticles of Comparative Example 2 were placed in sample tubes, and 1 ml of deionized water was added to each sample tube. The three dispersions were prepared using a probe ultrasonicator with an ultrasonic power of 75 W and an ultrasonic time of 15 s. The dispersions were left to stand for 0 days (initial state), 5 days, and 10 days, and photographed and recorded. The results are shown in FIG. Figure 3 As shown. Figure 3 It can be seen that the color of the Ga nanoparticle dispersion of Comparative Example 2 changed from the initial gray to white after standing for 5 days and 10 days, while the color of the BP-modified Ga (BP@Ga) nanoparticle dispersion of Example 4 did not change and remained gray. The color of the BP nanosheet dispersion of Comparative Example 1 also did not change and remained gray.

[0075] Furthermore, SEM was used to test the changes in the microstructure of the particles in the Ga nanoparticle dispersion of Comparative Example 2 and the BP-modified Ga (BP@Ga) nanoparticle dispersion of Example 4 over time. The test results are shown in Figures 4 and 5. Figure 5 As shown in FIG, the Ga nanoparticles in the Ga nanoparticle dispersion of Comparative Example 2 changed from spherical to rod-shaped after 5 and 10 days, and the particle size changed from 100-400 nm to 600-800 nm, indicating that the Ga nanoparticles are unstable and the morphology and size of the nanoparticles have changed; while in Figure 5 The particles of BP-modified Ga (BP@Ga) nanoparticle dispersion are dispersed on BP nanosheets. The morphology of Ga nanoparticles has not changed significantly, and the particle size remains at 100-400 nm, indicating that BP nanosheet-modified Ga nanoparticles can prevent Ga from being oxidized. In addition, the morphology and size of BP nanosheets have not changed.

[0076] The phase structure and composition of the particles in the BP-modified Ga (BP@Ga) nanoparticle dispersion of Example 4, the BP nanosheet dispersion of Comparative Example 1, and the Ga nanoparticle dispersion of Comparative Example 2 were measured by XRD and Fourier transform infrared spectroscopy after 10 days. Figure 6As shown, the Ga nanoparticles of Comparative Example 2 were transformed into gallium oxyhydroxide after being soaked in deionized water for 10 days, the BP-modified Ga (BP@Ga) nanoparticles of Example 4 remained in the phases of Ga and BP after being soaked in deionized water for 10 days, and the BP nanosheets of Comparative Example 1 also remained in the phase of BP after being soaked in deionized water for 10 days.

[0077] The total antioxidant properties of the BP nanosheets of Comparative Example 1, the Ga nanoparticles of Comparative Example 2, and the BP-modified Ga (BP@Ga) nanoparticles of Example 4 were qualitatively tested after being immersed in deionized water for different times. The lighter the color of the ABTS detection reagent, the better the total antioxidant property. Figure 7 As shown, the BP-modified Ga (BP@Ga) nanoparticles of Example 4 have better overall antioxidant properties than the BP nanosheets of Comparative Example 1 and the Ga nanoparticles of Comparative Example 2, and still maintain excellent overall antioxidant properties after being immersed in deionized water for 30 days.

[0078] The BP nanosheet dispersion of Comparative Example 1, the Ga nanoparticle dispersion of Comparative Example 2, and the BP-modified Ga (BP@Ga) nanoparticle dispersion of Example 4, which were soaked for 0 days and 10 days, were taken, respectively. The precipitates were collected after centrifugation. The precipitate particles were ultrasonically dispersed (power 75w, time 15s) in 1ml PBS solution, and the solutions were irradiated with near-infrared light of 808nm and power 1w to test the photothermal properties of the BP nanosheets of Comparative Example 1, the Ga particles of Comparative Example 2, and the BP-modified Ga (BP@Ga) nanoparticles of Example 4. Figure 8 As shown, the BP-modified Ga (BP@Ga) nanoparticles of Example 4 soaked for 0 days have better photothermal performance than the BP nanosheets of Comparative Example 1 and the Ga nanoparticles of Comparative Example 2. The initial test temperature is 25°C. After 20 minutes of near-infrared light irradiation, the temperatures of the BP-modified Ga (BP@Ga) nanoparticles, BP nanosheets and Ga nanoparticles increase to 45.9°C, 37°C and 45.1°C, respectively. After 10 days of irradiation with near-infrared light for 20 minutes, the temperatures of the BP-modified Ga (BP@Ga) nanoparticles of Example 4, the BP nanosheets of Comparative Example 1 and the Ga nanoparticles of Comparative Example 2 increase from the initial 25°C to 45.8°C, 37°C and 35.7°C, respectively. It can be seen that the photothermal performance of the BP-modified Ga (BP@Ga) nanoparticles of Example 4 has long-term stability, and is significantly better than the stability of the photothermal performance of the Ga nanoparticles of Comparative Example 2. In addition, from Figure 8 It can also be seen that after four cycle experiments, the BP-modified Ga (BP@Ga) nanoparticles of Example 4 maintained the same photothermal performance after 0 days and 10 days of immersion, further proving that the photothermal performance of the BP-modified Ga (BP@Ga) nanoparticles has stable cyclicity.

[0079] In summary, the above results show that Ga nanoparticles modified with BP nanosheets have excellent long-term stability, photothermal properties and overall antioxidant properties, providing strong support for their application in the biomedical field.

[0080] The above are all preferred embodiments of the present invention, and are not intended to limit the scope of protection of the present invention. Therefore, any equivalent changes made based on the structure, shape, and principle of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for improving the stability of metal gallium nanoparticles, characterized in that: The method comprises the following preparation steps: S1. Preparation of black phosphorus nanosheets: black phosphorus was added to N-methylpyrrolidone and sonicated in an ice bath to obtain a dispersion. The precipitate was collected after centrifugation, washed, and freeze-dried to obtain black phosphorus nanosheets. S2. Preparation of modified metal gallium nanoparticles: adding liquid metal gallium to ethylene glycol, adding dilute hydrochloric acid, and then adding the black phosphorus nanosheets after ultrasonic treatment. After ultrasonic treatment in an ice bath, the precipitate is collected by centrifugation, washed, and freeze-dried to obtain metal gallium nanoparticles modified with black phosphorus nanosheets.

2. The method for improving the stability of metal gallium nanoparticles according to claim 1, characterized in that: Step S1. includes: S1-1. Grinding black phosphorus crystals into black phosphorus flakes; S1-2. The black phosphorus flakes were added to N-methylpyrrolidone and ultrasonically treated in an ice bath to form a dispersion; S1-3. The dispersion was centrifuged, and the precipitate was collected, washed, and freeze-dried to prepare black phosphorus nanosheets.

3. The method for improving the stability of metal gallium nanoparticles according to claim 2, characterized in that: In step S1-1, the black phosphorus crystals are ground into black phosphorus flakes with a particle size of less than 3 mm.

4. The method for improving the stability of metal gallium nanoparticles according to claim 2 or 3, characterized in that: In step S1-2, the mass volume ratio of black phosphorus flakes and N-methylpyrrolidone is 10-30 mg:10-60 ml.

5. The method for improving the stability of metal gallium nanoparticles according to claim 2 or 3, characterized in that: In step S1-2, the ultrasonic treatment power is 50 to 150 W, and the ultrasonic treatment time is 5 to 20 h; and / or; In step S2, the power of the ultrasonic treatment is 50 to 150 W, the time of the ultrasonic treatment is 0.5 to 6 h after the addition of dilute hydrochloric acid, and the time of the ultrasonic treatment is 0.5 to 6 h after the addition of black phosphorus nanosheets.

6. The method for improving the stability of metal gallium nanoparticles according to claim 1 or 2, characterized in that: The black phosphorus nanosheets have a particle size of 0.1 to 15 μm and a thickness of less than 100 nm.

7. The method for improving the stability of metal gallium nanoparticles according to claim 1 or 2, characterized in that: In step S2., the mass-to-volume ratio of the liquid metal gallium, ethylene glycol, dilute hydrochloric acid, and black phosphorus nanosheets is 30-50 mg: 20-80 ml: 10-40 ul: 5-15 mg.

8. The method for improving the stability of metal gallium nanoparticles according to claim 7, characterized in that: In step S2., the mass-to-volume ratio of the liquid metal gallium, ethylene glycol, dilute hydrochloric acid, and black phosphorus nanosheets is 35-45 mg: 30-50 ml: 15-25 ul: 8-12 mg.

9. The method for improving the stability of metal gallium nanoparticles according to claim 1 or 2, characterized in that: In step S2, the particle size of the metal gallium nanoparticles is 100 to 400 nm.

10. Metal gallium nanoparticles with high stability, prepared by the method for improving the stability of metal gallium nanoparticles according to any one of claims 1 to 9.

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